pH and ORP

Learning Handbook

TI 12B00A20-01E
Table of Contents

1 Introduction.................................................................................................................4

2 Basics on pH theory.................................................................................................... 4

2.1 Concept of pH........................................................................................................................................... 4

2.2 The pH scale.............................................................................................................................................5

2.3 Measuring the pH scale..........................................................................................................................6

2.4 Principle of potentiometric pH measurement....................................................................................7

2.5 Hydrogen electrodes, the basic principle............................................................................................7

2.5.1 Composition of the glass electrode..............................................................................................9

2.5.2 Composition of the reference electrode......................................................................................9

2.5.3 The measuring circuit with a glass and a reference electrode..............................................10

2.5.4 More information about the glass electrode............................................................................ 11

2.5.5 More information about the reference system........................................................................12

2.5.6 Construction of the temperature electrode..............................................................................15

2.5.7 The combined pH sensors............................................................................................................15

2.6 The effect of temperature ...................................................................................................................16

2.7 Isolation resistance...............................................................................................................................18

2.8 Buffer solutions......................................................................................................................................18

2.9 Periodic maintenance and calibration of pH sensors......................................................................19

2.10 Differential electrodes..........................................................................................................................23

3 Basics on ORP............................................................................................................ 28

3.1 Concept of ORP......................................................................................................................................28

3.2 The ORP Scale.........................................................................................................................................28

3.3 Measuring the ORP Value.....................................................................................................................29

3.4 Composition of the Measuring Electrode..........................................................................................31

3.5 Composition of the Reference Rlectrode...........................................................................................32

3.6 The Measuring Circuit...........................................................................................................................32

3.7 Standard ORP vs pH Compensated ORP............................................................................................32

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 3.8 Standard Maintenance and Calibration..............................................................................................33

4 Product and Features............................................................................................... 36

4.1 Electronics/ Transmitters/ Converters...............................................................................................36

4.2 Sensors/ Electrodes...............................................................................................................................39

5 Lifespan and storage of electrodes........................................................................ 46

5.1 Recommended storage guidelines pH electrodes...........................................................................46

5.2 Recommended storage guideline.......................................................................................................46

6 Troubleshooting and diagnostic.............................................................................. 48

6.1 Errors resulting from cracked membranes...............................................................................................48

6.2 Fouling of the pH sensor......................................................................................................................48

6.3 Prevention of the reference electrode fouling..................................................................................49

6.4 Poisoning of the reference electrode.................................................................................................49

6.5 Errors caused by damped or electrode cable and connection.......................................................50

6.6 Errors caused by shorting the electrode cables...............................................................................50

6.7 Interferences by stray voltages in the liquid.....................................................................................50

6.8 Errors caused by poor installation......................................................................................................50

7 Frequently Asked Q&A............................................................................................... 51

8 Appendix 1:

Chemical Compatibility.........................................................................................................................60

9 Appendix 2:

Definitions...............................................................................................................................................64

10 Appendix 3:

Liquid Application Data sheet..............................................................................................................66

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 1. INTRODUCTION
Measuring pH/ORP is very common, but taking true measurements and correct interpretation of the results is not
1. INTRODUCTION

self-evident. Certain effects can potentially cause problems if not taken into consideration.

The purpose of this book is to provide a comprehensive understanding of pH/ORP measurement and how to achieve
reliable results. Basic information on the principles of measuring pH/ORP, the construction of the sensing elements
and their basic use in process applications are provided.

A part of achieving accurate and reliable pH/ORP measurements requires sufficient and correct maintenance and
storage conditions. Prevention of common errors during maintenance and storage, as well as consistent detection of
loop failures is important. This book describes how these can be avoided and how failures can be detected.

This book is accompanied with a frequently asked question and answer section, as well as an appendix that includes
helpful information like a Chemical Compatibility Table and a Liquid Application Data Sheet, which can be used to
describe the user’s application.

In brief: This book will make your job easier!

2. Basics on pH theory

T
2.1 Concept of pH
he Danish scientist Sørensen other factors, such as:
defined the concept of pH as
follows: ■ The activity of other ions present
in the solution
pH equals the inverse of the logarithm ■ The temperature of the solution
to the base 10 of the hydrogen ion
concentration, as shown by the ■ The character of the solution.

To facilitate the accurate

formula:
pH = -10log [H+ ] = paH1) (1)
Later Sørensen found this definition
to be incorrect, since more
concentrated solutions appeared to
give deviations between calculated
and measured values.
The definition therefore, had to be
modified to:
pH equals the inverse of the logarithm
to the base 10 of the hydrogen ion
activity2) as shown by the formula:
measurement of pH, and its
presentation as a scale, a range
of “standard liquids” or “buffer
solutions” are used.
These liquids, whose constituents
are accurately defined, have known
stable values.
Although in the preceding text the
relationship to hydrogen ions has
been made, research has shown
that the activity of hydroxonium
ions (H30+ ) is more relevant. In
aqueous solutions, free H+ ions
Søren Peder Lauritz Sørensen
do not occur, but are always in
combination with water molecules. (1868-1939)

pH = -10log aH+ = pH ) 3
(2)
The activity of the hydrogen
ions is not always linear with
the concentration, since this
Born in Havrebjerg, Denmark,
H+ + H2O ↔ H3O+ Sørensen was a Danish chemist,
famous for the introduction of the
concept of pH, a scale for measuring

activity is not only affected by the Consequently, a more correct acidity and basicity. From 1901 to 1938

concentration of ions, but also by
Note 1. The notation -10log .... can also
be written p ....
Note 2. See appendix 2: Definitions.
Note 3. See Chapter 2.8: Buffer
solutions.
definition for pH is:
pH = -10log aH3O+ (3)
For clarity, the notation H+
will be used in the book as the
hydroxonium ion.
he was head of the prestigious Carls-
berg Laboratory, Copenhagen.While
working at the Carlsberg Laboratory
he studied the effect of ion concen-
tration on proteins,and because the
concentration of hydrogen ions was
particularly important, he introduced
the pH-scale as a simple way of
expressing it in 1909.

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2.2 the pH Scale
Your starting point for the pH scale
is pure water, which is said to be
neutral. Water dissociates1) into:

H2O ↔ H+ + OH– (4)

Water has an equilibrium constant 2)3):
Pure
[H+] . [OH–] wate
Kw = = 10–14 (5) r
[H2O]

or:

2. BASICS ON pH THEORY
-log Kw = pKw = -log [H+] + -log
[OH-] = 14 log 10 (6)

Pure water divides to give equal

numbers of H+ and OH– ions and Fig. 2.2a. pH value of pure water against temperature.
consequently, the concentrations of
ions are 10–7 so that:
solutions with an acid character are: T( C)
T(ºC) pKw
pKw pH
pH
pH = pOH = 7 0 14,94 7,47
H2S04 ↔ S042 + 2H
– +
The pH value of pure water is 7. 18 14,22 7,11
This statement is incomplete, since Sulphuric acid
the equilibrium constant depends HCI ↔ CI + H
– +
25 14,00 7,00
on the temperature. Hydrochloric acid 50 13,22 6,61
If the concentration of OH– ions in a 100 12,24 6,12
The definition should be: The pH
solution is increased (e.g. to 10–10)
value of pure water is 7 @ 25°C.
then the solution is said to have a
Figure 2.2a. and the table show base character.
the pH variation of pure water with Note 1. See appendix 2: Definitions
In this case the pH value of the
temperature. Note 2. The equilibrium constant is
solution is a number greater than 7.
the ratio between the rate of
If the concentration of H+ ions
in a solution is increased (e.g. to Some more examples are: decomposition and the rate of
composition.
10–4), then the solution has an acid
character. In this case the pH value Note 3. The concentration H20 is
NaOH ↔ Na+ + OH
–
is lower than 7. supposed to be 1.
Caustic soda
Some examples of common NH3 + H2O↔ NH4+ + OH
–

Ammonia aqueous ammonia

pH Table
Some examples of the difference in These can be compared with the
the pH value of various liquids, foods pH values of common chemical
and fruit are shown in Figure 2.2b. compounds dissolved in water.

A L K A L I NI TY

Fig. 2.2b.

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 2.3 Measuring the pH Scale
The pH value can be measured by
different methods, e.g.:

A. Colorimetric pH measurement

B. Potentiometric pH measurement

2.3.1 Colorometric pH Some examples are: Some natural indicators are:

measurement
Litmus paper Red cabbage
The principle of colorimetric
When immersed in an acid medium Red cabbage is red in a acid medium
2. BASICS ON pH THEORY

determination of the pH value is based

on the pH dependance of color change.
the paper shows red and it
changes to blue in a base medium.
“pH paper” consists of paper
impregnated with a suitable dye.
After immersion in the liquid to
be measured, the color of the wet
paper can be compared with a color
disc which shows the relevant pH
value for the varying shades of color.
and blue/violet in a natural medium.
In an strongly basic medium the
color changes to green.
Mushrooms will whiten considerably
by treating with vinegar (an acid). In
a base medium the mushrooms will
turn brown.
2.3.2 Potentiometric pH

measurement sensor method (ISEFT)

The most often used pH sensing ISEFT is a non-glass, ion-sensitive

element is a pH sensitive glass
sensor. Other pH sensors are
used if a glass sensor is not
acceptable (e.g. antimon sensor,
ISFET).
Accurate potentiometric pH will
be discussed in more depth in
later chapters.
semiconductor device (or transistor)
used to measure the changes in ion
concentrations within a solution.
The current that passes through the
transistor will change in response to
the ion concentration change.

2.3.3 The semiconductor

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2.4 PRINCIPLE OF POTENTIOMETRIC pH MEASUREMENT
The principle of potentiometric pH
measurement can be explained by
Nernst’s law.
Walther Hermann Nernst
(1864-1941)
Born in Briesen, West Prussia, in
1864. He spent his early school years
(Gymnasium) at Graudentz, and sub-
sequently went to the Universities of
Zurich, Berlin and Graz (Ludwig Boltz-
mann and Albert von Ettinghausen),
studying physics and mathematics.
2.5 Hydrogen electrode, the basic principle
Fig. 2.5a The “hydrogen electrode”
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Nernst found that a potential
difference occurs between a metal
object and a solution containing
ions of the same metal when the
object is immersed in the solution.
The potential difference E, caused
by the exchange of metal ions
between metal and liquid, was
defined by Nernst as follows:
E = Eo + RT. In [Mn+] (7)
nF
R = Gas constant (R=8.314J/mol.K)
F = Farady number (F = 96493 C/
mol.)
n = Valency of the metal
[Mn+] = Metal ion concentration
T = Absolute temperature in Kelvin
Eo = “Normal potential”
Around 1906 Max Cremer found that
some types of glass gave a potential
difference of which the magnitude
depends on the acid value of
the liquid in which the glass was
immersed.
Later, Fritz Haber and Zygmunt
Klemensiewicz proved that this
potential difference, within a fixed
pH range, followed Nernst’s law in
the same way as with the so called
“hydrogen electrode.”
Glass can be considered as
an “undercooled” electrolyte
consisting of an irregular structure
(Si02) and a number of other
components which move in the
interspaces. These components
commonly consist of Na+ ,Ca2+ or
Li+ -ions and give an electro-balance
of the glass membrane
(see figure 2.5a).
The “normal potential” is the
potential diffe­rence arising between
metal and solution when this
solution contains 1 mol Mn+/litre.
Since the behavior of the gas
hydrogen has a certain degree of
conformity with a metal (both have a
positive ion formation), Nernst’s law
can also be applied to a “hydrogen
electrode”1) immersed into a
solution con­taining hydrogen ions.
2. BASICS ON pH THEORY
The formula can be re-written as
follows:
E = Eo 2) + RT. In [H+] (volt)
nF
or:
With the constants:
E = Eo + 0,059 Ln [H+] (volt)
Note 1. A
 “hydrogen electrode” can
be made by coating a layer of
platinum-black on a platinum
electrode and passing a flow
of hydrogen gas over it. The
presence of platinum-black
results in the hydrogen
gas being adsorbed on the
electrode resulting in a so-
called “hydrogen electrode”
(see: Figure 2.5a).
Note 2. By definition, the normal
potential E of the metal
“hydrogen” in a 1 normal
H+ solution is 0 volt at all
temperatures.
7

2. BASICS ON pH THEORY
When immersed in aqueous solutions,
all types of pH glass have the
particular property to exchange the
metal -ions of the glass texture against
the H+ ions in the solution.
Since the H+ are bounded to a H2O
molecule and not free, the texture
of the siliceous acid will be defound
during the exchange by the bigger
H3+ -ion.
As a result of this reaction a so-called
“gel-layer” will be developed on the
surface of the glass membrane. This
gel-layer is the equivalent of the metal
in the Nernst’s theory, and is therefore
essential for the functioning of the
glass sensor.
After one or two days the condition
reaches equilibrium and the resulting
gel-layer has a thickness between 10
and 40 nanometers.
8 www.yokogawa.com
This depends on several factors,
such as the composition of the glass
and the temperature in which the
sensor is immersed.
The voltage development across
the glass membrane is generally
explained by means of the phase
limit potential theory 1).
After reaching the equilibrium the
hydrogen concentration (=activity)
outside the glass and inside
the gel-layer are equalized, and
consequently, no transport of H+
ions occurs. The voltage across the
glass membrane is 0 volt.
If the concentration of hydrogen
ions in the two phases differs from
the concentration in the solution,
a transport of hydrogen ions takes
place.
La+++ 115x10–10 m
Ba++ 1,35x10–10 m
Ca++ 0,99x10–10 m
Cs+ 1,69x10–10 m
Li+ 0,6x10–10 m
O– – 1,4x10–10 m
Si++++ 0,4x10–10 m
Fig. 2.5b. Texture of pH glass
The movement of the ions will affect
the neutrality of the gel-layer. As a
result, a voltage will be developed
preventing the further transport of
H+ ions.
The value of the voltage depends
on the concentration of the
hydrogen ions in the solution. Since
this voltage cannot be measured
directly, it will be necessary to
add a pH independent reference
potential in the measuring circuit.
This addition allows measurement
of the potential differences across
the glass membrane.
Note 1: For clarity, other theoretical
explanations like the theories
of the adsorption potential,
membrane potential and
statistic mechanic will not be
explained.
2.5.1 COMPOSITION OF THE GLASS ELECTRODE
Normally the glass electrode has a membrane designed as follows.
bulb shaped membrane of specific
“pH glass” that is “welded” to the -B
 all Shape (Shockproof)
Gold

This is a universal electrode

O connector
glass tube. The bulb is filled with a
“buffer” solution. A reference pin is suitable for most pH
fitted and protrudes into this liquid. applications.
The complete reference system
Contact is completely separated from - Dome shape
spring
the other parts of the electrode The mechanically very strong
and is connected to the plug of pH membrane (thickness
Metal the electrode via a platinum wire approx. 1 mm) is extremely
screen
welded in glass. suitable for measurements in
aggresive media.

2. BASICS ON pH THEORY
Consequently, it is impossible for
the buffer liquid to penetrate the - Flat shape
Contact
other parts of the electrode. This design is used in combined
sensors for application where
spring

As the glass membrane has a solids are a considerable

high-impedance resistance, an component.
integral metal screen which also
carries a printed code denoting
Reference pin
Note: For a better understanding,
Bending glass
applications, is fitted to prevent the construction of the glass
pick-up of electrical interference. electrode and reference
electrode are being shown as
the single electrodes before
Alternatives to the standard bulb
Buffer liquid
describing the complete
version of the “pH sensitive glass
pH sensitive
measuring circuit. Today
membranes” are available.
membrane
these single electrodes can be
combined in one pH sensor for
Yokogawa has developed the most applications, which
Fig. 2.5.1. The glass electrode

electrodes with the pH sensitive be shown later.

2.5.2 COMPOSITION OF THE REFERENCE ELECTRODE

Gold Nernst found that the combination A constant flow of electrolyte from
O connector of a metal and its insoluble salt in a the electrode pre­vents poisoning of
salt solution produces a constant mV the electrolyte around the reference
potential. pin.

When such a combination (known The reference system in the

as a reference sys­tem) is immersed
Metal-glass directly in a process liquid, variations
junction
may occur as a result of other ions
Reference pin which may be pre­sent in the liquid.
Furthermore, the reference system
Cotton wool
reference electrode is joined to
the gold cable connector with a
platinum pin fused in the glass.
By means of the reference
electrode, it is possible to measure

Glass tube may be poisoned by the penetration the pH dependent potential of the
of “unwanted ions” in the salt glass elec­trode very accurately.
solution. To overcome this problem
Electrolyte

an eletrolyte and dia­phragm is used

Note: This potential is temperature
to connect the metal/metal salt with
dependant.
the process liquid (see Figure 2.5.2).

Diaphragm

Fig. 2.5.2 The reference electrode.

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 2.5.3 THE MEASURING CIRCUIT WITH A GLASS AND A REFERENCE ELECTRODE

The diagrams show a pH

measuring circuit using a
A
E8 A-B
Yokogawa pH analyzer. It consists
E7 Fig. 2.5.3a and 2.5.3b
Measuring circuit.
of the pH glass electrode,
reference electrode, solution
E6
B
ground and pH analyzer built
Et

E3
as dual amplifier system. The
E4
diagrams show the potentials
which a ffect the final potential
R elecrolyte

difference (Et) between the glass

R elecrolyte
E2
E5
electrode and the reference
electrode.
R membrane

R diaphragm
2. BASICS ON pH THEORY

E1
R
E5 E4 E1 E2 E3 liquid

The following potentials are the most significant:

E1 = p
 otential difference between the pH sensitive glass membrane and the liquid to be measured.
E2 = p
 otential difference between the electrolyte in the glass electrode and the inner face of the glass membrane.
E3 = potential difference between the electrode pin and the electrolyte in the glass electrode.
E4 = p
 otential difference between the electrolyte and the electrode pin in the reference electrode.
E5 = p
 otential difference that occurs at the interface of two liquids with different concentrations, namely the electrolyte and the
process liquid.
E6 = potential difference between pH element and solution ground at Input B of dual amplifier.
E7 = potential difference between reference element and solution ground at Input A dual amplifier.

The total sum (Et) of these potential
differences is measured by the pH-
Analyzer:
Et = E 1 + E 2 + E 3 + E 4 + E 5 (8)
Potential (E6) is the potential of pH
electrode against solution ground:
E6= E1-E2 -E3
Potential (E7) is the potential
of Reference electrode against
solution ground:
E7= E4 + E5
Cz- = concentration of the salt solution
The equation (8) will then be
simplified to:
Et = E1+ E2+ E5 (9)
With correct selection of the
electrolyte used in the reference
electrode and a good flow through
the liquid junction, the potential
difference E5 can be neglected, so that
Et = E1 + E2 (10)
The ideal conditions described
above cannot always be completely
realized in practice. A small
potential difference may exist
when the glass and the reference
electrode are both immersed in a
liquid of similar properties and pH
value to the electrolyte.
Et = 0.05916 (pHinner- pHouter) + Easy (13)
This potential difference is called
the asymmetric potential of the
measuring system.

E1 = Eo + RT. In [H+]outer (11) The asymmetric potential Easy may

As we are only interested in the F
potential difference between the be caused by:
glass membrane and the process Or
- The liquid diffusion potential (E5
liquid to be measured (E1), the
E1 = E - 0.05916 • pHouter ≠ 0).
remaining potentials must be
o

compensated for so they do not The potential difference is the result

affect the true pH measurement.
Re-examination of the potentials
generated shows that:
If the reference systems in the glass
and the reference electrode are
identical and they are at the same
temperature1), then the potentials
(E3 and E4) generated by each are
equal but opposite:
E(3)=E4 ==> E(3) -E4=0
The potentials E3 and E4 are defined
as follows:
in the same way E2 can be defined as:
E1 = Eo - 0.05916 • pHinner
Since E1 and E2 in the pH measuring
loop are of opposite polarities the
equation becomes:
Et = E 2 - E 1
Et = 0.05916 (pHinner - pHouter)
RT.
The potential is kept
F pHinner
constant by filling the glass electrode
with an electrolyte with good buffer
of concentration differences across
the flow diaphragm and is called the
diffusion potential difference.
- The inner and the outer faces of
the pH sensitive membrane vary
because of differences in glass
texture which occur during the
glass blowing.
(12) E1 + E 2 ≠ 0
Note: 1. S
 ee chapter 2.6: “The effect of
temperature”.

E= ENe
o
+ RT • In LmZ properties and consequently, the Note: 2. Errors resulting from Easy
F Cz- measured E1 now only depends on the are compensated for during
in which potential difference between the glass calibration using buffer solutions.
membrane and the process liquid.
Lmz = solubility product of sparingly
soluble salt

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 2.5.4 MORE INFORMATION ABOUT THE pH GLASS ELECTRODE
The correct selection of a glass ■ sensitivity of the glass electrode To facilitate this process, it is
electrode for a particular application (mV/pH) necessary for the pH sensitive glass
can only be made if details of the ■ alkaline error membrane to be “conditioned” by
components of the measuring loop ■ acid error allowing it to absorb a film of water or
and their significant properties are ■ chemical resistance of the glass gel-film.
known. The following points will be membrane
considered in detail: ■ electrical resistance of the glass Conditioning is achieved by soaking
membrane the electrode in water for a minimum
■ selection of the glass membrane of 24 hours.
2.5.4.1 Selection of
the glass membrane The selection of the correct type of
135

glass electrode depends on both

L-Glass
- High temperature

The glass membrane the type and thickness of the glass

- Alkaline

reference is an membrane. Two types of glass are

important part of the available, as described here:

2. BASICS ON pH THEORY
100
complete pH measuring
70 loop. pH sensitive ■ “G” glass - This is used for the
glass has the particular membranes of electrodes in pro­
property that alkali cesses where the nominal pH value
Temperature (ºC)

metal ions present varies around pH 7. Since this type of

in the texture of the glass has a wide application ran­ge it is
G-Glass glass when they are also termed “general purpose” glass.
- General purpose
exchanged with H+ ions
0 of the liquid. ■ “L” glass - The application of “L” glass
0 pH 10 14 is for measurements in alkaline media
with high process temperatures.
Fig. 2.5.4. Types of pH sensitive glass and their applica­tion ranges.

Note 1: T
 he diagram shown in Figure2.5.4 is intended to assist with
selection of the most suitable type of glass electrode in
conjunction with the application range shown for each type.
The range of any particular glass type also depends on the
membrane thickness. Three different thicknesses are available.
Note 2: Glass electrodes manufactured by Yokogawa are
“preconditioned” and may be used immediately without
soaking. To form and maintain the gel-film, the sensitive glass
bulb is protected with a rubber containing a small quantity of
water which forms a wet pocket for the membrane.

2.5.4.2 Sensitivity of the glass
electrode
The most important requirement
in any electrode system for pH
measurement is that the actual mV/
pH ratio genera­ted is as close as
possible to the theoretical value.
The potential generated by a glass
electrode is given by equation:
E=
RT. . 2,303 (pH
nF
inner
At a temperature of 25°C the equation
becomes:
E = 59,16. 298 . (pHinner – pHouter)mV 298
273+25
In the equation pHouter is the pH value
of the liquid at the outer face of the
glass membrane and pHinner is the
slope, at the analyzer. The decrease
in sensitivity is usually caused by
fouling of the glass membrane. It is
of the greatest importance that the
electrode is properly cleaned before
“buffering” and adjustment for
sensitivity is made.
If the electrode has been stored dry
for a long period the sensitivity will
Note: The electrode must be cleaned
– pHouter) mV carefully before and after
activation. (For cleaning and re-
activation see: “Direction for use”
enclosed with each electrode).
Frequent re-activation decreases
the life of the electrode.
Sodium Error
0
not reach an optimal value until the
electrode has been conditioned for a
number of hours.
When the decrease in sensitivity
is caused by aging of the glass
membrane the electrode can be re-
activated by etching the surface of the
glass membrane.
This should be done by immersing the
electrode for 10 seconds in a solution
of vinegar (1 mol.) and potassium
fluoride (1 mol.). Ratio 1:1
2.5.4.3 Alkaline of the glass
electrode
In addition to a correct mV/pH ratio,
it is essential that the generation of
potential difference is only
influenced by the activity

value of the electrolyte at the inner of the H+ ions and not by

face of the membrane. the presence of the other
-50

monovalent cations such as

The mV/pH ratio is called the
-1 00

Li+, Na+, etc.

sensitivity or slope of the electrode.
-1 50

A low concentration (or

U [mV]

The quality of the glass membrane

-2 00
activity) of H+ions (typically
is the most important factor
U [mV]
a pH value of 13) and a high
-2 50

in achieving correct electrode activity of alkaline ions may

sensitivity.
-3 00

cause measuring errors of

between 0.5 to 1.0 pH.
-3 50

Reduction in sensitivity of glass

electrodes may be compensated for
-4 00
pH
by adjustment of the mV/pH ratio or
7 9 11 13

Fig. 2.5.4.3 Alkaline and acid errors of the glass electrode.

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 In practice, the alkaline error
is often caused by sodium and
consequently the term “sodium
error” is also used to describe this
effect.
The alkaline error can be
considerably reduced by making
certain additions to the pH
sensitive glass, which improves
the selectivity of the electrode. In
Fig 2.5.4.3 the alkaline error of the
different types of glass at varying
pH values are shown.
As well as affecting the selectivity,
2. BASICS ON pH THEORY
the aforementioned additions also
influence other properties, such
as chemical resistance and glass
resistance.
2.5.4.4 Chemical resistance of
the glass membrane
The chemical resistance of the glass
membrane is greatly influenced
by the process conditions. High
temperatures and high salt
concentrations or applications in
strong alkaline liquids generally
shorten the electrode life.
Additives can be included during
the manufacturing of the glass that
make it more resistant to attack,
and consequently electrodes can
be produced that are suitable for
2.5.5 More information about the Reference System
2.5.5.1 General
In earlier chapters the various
requirements for glass electrodes
to give accurate pH measurements
are described in detail.
The accuracy of the measurement
also depends on the properties
of the reference electrode used.
It is important therefore, to
describe the different properties
of reference electrodes so that a
correct selection can be made.
A good reference electrode
satisfies the following
requirements:
■ the output voltage is
determined by Nernst’s law
■ the output voltage is stable.
In the description below the
different types of reference
systems, the flow diaphragms, and
the electrolytes used in reference
electrodes, are all discussed.
12
measurements in either strong acid
or strong basic liquids. In aggressive
solutions, a heavy duty electrode
with a thick, dome-shaped glass
membrane is preferable.
2.5.4.5 Electrical resistance of
the glass membrane
Since glass is a good insulator,
potentiometric measurements
cannot be obtained with normal
glass, and constituents must
be added which will reduce the
membrane resistance below
1000 MW to minimize the effect
of electrical disturbances on the
measurement.
The composition of the glass, its
thickness, the surface of the glass
membrane and the temperature,
all affect the value of the glass
resistance.
Typical resistances of glass
electrodes with shock-proof bulb
membranes at 25°C, are as follows:
Type of glass Membrane resistance
G-glass 50-100 MW
L-glass 300-500 MW
The thickness of the glass bulb of G
glass affects the electrical resistance,
as follows:
The application range
and specification are
shown in table 2.5.5.2.
Metal
Glass Junction
Silver coated with
Silver chloride
Normal
Bulb shaped (shock-proof):
50-100 MW
Dome shaped (heavy duty): 120-200
MW
2.5.4.6 The response time of
the glass electrode
The response time of a glass electrode
indicates the ability of an electrode to
follow accurately any changes in the pH
value. The response time is normally
defined as the time taken to reach 63% of
the value of a step change in input. Since,
in practice, the response time depends
on a lot of factors e.g.: the reference
electrode used, the conductivity of a
liquid, the temperature, the position of
the electrode in the process, the process
flow, the flow speed, etc. the response
time quoted for a particular type is only
an approximation.
Example: Glass electrode, type SM21-
AG4 (shock-proof membrane).
pH change 63% of the end scale
value is reached after:
1.68 to 7 5 seconds
7 to 1.68 5 seconds
Metal
Glass Junction
Mixture
of Ag + AgCI
Cotton Wool
High temperature
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2.5.5.2 Reference system
Generally, the reference system
used in reference electrodes, are:
Silver/Silver chloride-Potassium
chloride: (Ag/ AgCI-KCI)
This reference system consists of
Type of reference system
Silver chloride wire (AgCI) in 1 molal KCI
Silver chloride paste (AgCI) in 1 molal KCI
Silver-silver chloride in saturated KCI
2.5.5.3 Junctions of
the reference
The selection of the correct type of
junction of a reference electrode
depends on the process conditions
under which the electrode has to
function.
The following junction types are
available: (see Figure 2.5.6).
1.Ceramic junction.
2.Ceramic junction.
3.P.T.F.E. junction.
4.Glass sleeve capillary element.
The purpose of the junction is to
maintain contact between the
reference system in the electrode
and the process liquid.
When selecting the correct
junction, consideration has to be
given to ensure that the process
liquid does not penetra­te into the
electrode causing poisoning and
a consequential unstable liquid
junction potential.
With the first two types of junction
listed above, the KCI solution flows
slowly into the process. The flow
rate is dependent on the over-
pressure in the electrode and on the
process temperature.
The electrolyte flow rate increases
with increasing temperature.
For use in very dirty liquids a glass
sleeve capillary element is preferred
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a silver wire electro­lytically coated This paste is sealed into a tube by
with silver chloride. This metal - means of a plug wadding soaked in
metal salt combination is dipped in KCI.
a potassium chloride so­lution (KCI).
This reference assembly is similarly
A second type of construction for dipped in a KCI so­lution.
this system consists of a silver wire
dipped in a paste of silver chloride,
silver and potassium chloride.
Output voltage with regards to H2
Application range/remarks
electrode at 25°C
+223 mV ±5 mV upto 100°C
2. BASICS ON pH THEORY
+230 mV ±5 mV upto 120°C
+198 mV ±5 mV upto 120°C
1 2 3 4
Ceramic Ceramic PTFE Sleeve
Fig. 2.5.6
because of its larger flow surface. diaphragm at equal speed
The sleeve can be easily cleaned
by first moving the ground ring ■ having a low electrical resistance
upwards and then wiping the The most common electrolyte used
ground faces. in reference electrodes are:
Non-flowing reference electrodes ■ 1moal KCL solution (with or
with a porous P.T.F.E. junction can without gel)
also be used in many dirty liquid
■ 3.3 molal KCI solution
applications. The dirt resistant
properties of P.T.F.E. will prevent ■ saturated KCI solution.
complete fouling of the diaphragm.
2.5.5.4 Electrolytes in the
reference electrode
The electrolyte in the reference
electrode must satisfy the following
requirements:
■ chemically inert and neutral
■ no reaction with the process
liquid
■ having a constant activity of ions
■ equitransferent, i.e. the ions of
the electrolyte must pass the
13
 2.5.5.5 Pressure compensated
reference electrode
In processes with pressure
Reference variations, the composition of the
system electrolyte may change as a result of
process liquid penetration into the
electrode.
Any change in composition of the
electrolyte may cause a measuring
error or even poisoning of the
reference system of the electrode.
The pressure inside the bellows equals
the pressure outside and only the
elasticity of the bellows itself causes
the over-pressure, which results in a
flow of electrolyte.
When the bellows are fully “expanded”
the electrolyte is exhausted and
refilling is required. The bellows must
be compressed before refilling.

To alleviate this problem, an

Bellows

electrode with an integral pressure

2. BASICS ON pH THEORY

compensation system (SR20-AC32)

may be the solution. See figure
Electrolyte 2.5.5.5.

Integral pressure compensation

systems operate in a way where the
electrolyte vessel of the electrode
contains bellows which are
compressed in the working position.
One side of the bellows is connected
Process to the pressure via the ceramic
pressure junction and at the other side via the
Flow inner tube.
diaphragm
Note: T
 he pressure compensated
reference electrode can al­so
be used in processes with
Fig. 2.5.5.5 Pressure compensated pressures below atmo­sphere.
reference electrode (SR20-AC32)

2.5.5.6 Reference electrode Mostly, a black diaphgram indicates

with built-in salt bridge by
Gold
O connector that the reference electrodes is used
using double junction without a double junction.

In chapter 2.5.5.4 it is explained The black is a deposit of silver

that the electrolyte in the re­ference
Metal-glass junction electrode may not be changed by
penetration of the process liquid.
Reference system
sulphide in or directly after the flow
diaphragm.
The results of such deposits can be:

Example: Mercury (Hg22+), Copper

Cotton wool
Glass reservoir for
(Cu+), Lead (Pb2+) and Silver (Ag+) ■ long response of the pH
measuring circuit
reference system
Electrolyte ions in the process liquid will give a
reaction to the KCI solution from the ■ non-reproducible diffusion
reference elec­trode. voltages and consequently drift
in the indication.
To solve this problem, the KCI
solution and the process liquid ■ calibration is hardly possible (the
formed diffusion voltage can be
Double junction
diaphragm (salt must be separated using a double
bridge)
junction electrolyte, resulting in a pH dependent).
Double junction reference electrode with a built-in ■ increased resistance of
Electrolyte
saltbridge. the diaphragm (slower
measurement).
Processes containing cyanides,
Flow bromides, iodides or sulphides are a
diaphragm
second example of selecting the KCI
solution critically.
Fig. 2.5.5.6 Reference
electrode with double
junction (SR20-AP24)
Note: Most biological process li­quids
contain sulphuric compounds.

14 www.yokogawa.com
2.5.6 Construction of the Temperature ELECTRODE

Gold pH measurements are temperature As an alternative to automatic

O connector dependent from two different temperature compensa­tion it is
effects: possible to manually compensate
for tempera­ture variations.
a. by the variations with
temperature on the contact
potentials in the glass and the
reference system.
Screen plate
b. by temperature variations of
the liquid being measured.

Therefore it is necessary to include

a temperature compensator in the

2. BASICS ON pH THEORY
system, whose purpose is to provide
Tube automatic compensation for the
effects of temperature variations on
the measuring system.

These compensators are made

in the same shape as the other
electrodes to enable them to be
mounted in the same fittings.
The temperature compensator
Pt100

consists of a platinum resistance

resistor

Thermal element (e.g. PT100, PT1000),

conducting mounted in a glass tube. The tube
is completely filled with white
grease

silicon grease, which has thermal

conducting properties to ensure
Fig. 2.5.6. The resistance thermometer fast temperature response.

2.5.7 The combined ph sensors

In today’s business we see a glass-, reference-, temperature The reference systems of both the
tendency to use combined sensors electrode and solution ground are glass and the reference electrode
instead of separate electrodes. In built into one unit. consist of an Ag/ AgCI with same
modern combined electrodes the KCL solution.

The operating principles are

Wide body sensor Glass sensor identical to those used for the
individual electrodes.

The advantage of combined sensors

is easy maintenance.

2 2 There has been a progression in

9 the design of combined sensors
3 1 from the ability to have just a pH
1 3
10 and reference in a 12 mm design, to
9 4 also incorporate the temperature
4 element and the solution ground.
Yokogawa has managed to fit all
10
electrodes into the 12 mm design
6 7 8 6 7 8 with the development of the SC24V
5 5 and SC25V sensors.
1 Reference electrode 5 pH glass electrode
2 Reference element 6 Internal reference element By incorporating the solution ground
3 Electrolyte 7 Glass membrane 9 Temperature element the possibilities for performance
4 Juction 8 Internal buffer solution 10 Solution ground improve, along with predictive
maintenance and diagnostic
Note: The Wide body sensor should be simplification of FU20. Glass sensor should be the capabilities have improved.
simplification of SC25.

Fig. 2.5.7. The combined pH sensors

www.yokogawa.com 15
 2.6 The effect of temperature
2.6.1 Temperature effect on
the glass and the reference
electrode
The glass and the reference
electrodes have a number of
temperature dependent contact
potentials; it is obvious then
that the voltage supplied by the
measuring system is temperature
dependent.
This temperature dependancy is
shown by the factor in the
2. BASICS ON pH THEORY
Nernst equation RT
F
The voltage supplied by the
measuring system is:
Et = Easy x 2,303 RT .(pHinner – pHouter)
F then by varying the temperature of
Et= Easy x 59,16 (T+273) (pHinner– pHouter)
298
pHinner is standardized at pH 7.
T is the temperature in °C
If the glass and the reference
electrodes are immersed in liquids
of equal temperatures, the potential
variations of similar reference
systems will be equal and opposite.
E3 = -E4
Consequently, the system will
be unaffected by tempe­rature
variations.
The temperature effect on the
contact potential of the junction on
the reference electrode is kept to a
minimum by correct selection of the
junction and electrolyte.
The temperature effects obtained
by immersing the electrodes in
different standard solutions and
2.6.2 Temperature effect on the process liquid
In the preceding chapter, the
temperature effect on the
measuring system and its
correction, have been considered.
In addition, however, a temperature
effect on the chemical balance of a
process itself.
It has been previously stated that
the pH value of pure water at 0°C
differs from the pH value at 100°C.
16
mV
–500 –400 –300 –200 –100
20ºC
60ºC
these standard solutions, are shown
in the graphs of Figure. 2.6.
This graph shows that:
a.The mV/pH ratio increases
as the temperature of the
measuring system increases.
At 25°C the mV/pH ratio is 59.16
and at 20°C this ratio is 58.16
mV/pH. At 80°C the mV voltage
per pH unit is increased to 70.08
mV.
b.The various isothermal
lines intersect at one point
S (the isothermal point of
intersection).
c.The intersection point is
dependent on the pH of the
buffer solution used in the
glass electrode (this is usually
pH 7). It is important that the
isothermal lines intersect at
only one point. So selection of
the correct buffer solution is
This is caused by a change of the
chemical balance.
H2O ↔ H+ + OH-
at 0°C for pure water
pK = 14,94 or pH = pOH = 7,47
at 100°C for pure water
pK = 12,24 or pH = pOH = 6,12
mV
0 +100 +200 +300 +400 +500
1
2 0ºC 80ºC
3
4
5
6
7
S
8
9
10
11
12
13
14
pH
Fig. 2.6 Temperature effect on the mV/pH ratio.
essential in order to obtain an
accurate isothermal point of
intersection S, shown in Figure
2.6.
In general, when a pH measurement
is made in a process at widely
fluctuating pH and temperature
levels, automatic temperature
compensation is necessary. To
achieve this the electrode system
is completed with a temperature
sensing element, packaged in
a similar construction to an
electrodethat compensates for
slope variations of the mV/pH ratio
of the electrode system.
Note 1.The isothermal point of
intersection of the standard
electrodes of Yokogawa is at
pH 7. Depending on the buffer
solution used this point may,
for special applications, be at
another value pH 3.
For accurate comparison of pH
values made by different techniques
(e.g. by lab, measurement and
industrial measu­rement), it
is necessary to state at what
temperature the measurement was
made.
As the effect of temperature on any
process liquid is highly dependent
on its composition, it is not possible
to accura­tely compensate for this
effect automatically.
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2.6.3 Temperature effect on the application range of the glass electrode

Process temperature is a major factor 10000

in the selection of the type of glass Glass Impedance
electrode to be used for a particular 1000
application. Different reference
systems are used for high or low
process temperatures.
100

MΩ
Furthermore, the chemical resistance 10
of the glass membrane is temperature
dependent and correct selection is 1
important.
0.1
A third factor is the membrane
resistance of the glass electrode. This

2. BASICS ON pH THEORY
increases considerably at lower process
0.01

temperatures and may increase the

-5 5 15 25 35 45 55 65 75 85 95 105 115 125
response time to an unacceptable level.

A rough guide is that the glass

membrane resistance increases by a AG2 (25M) AG4 (100M) AG6 (200M)
factor 2 with every temperature fall of
10°C. Figure 2.6.3 shows the resistance AL6 (1000M) HIGH LIMIT LOW LIMIT
of glass membranes for various species
of glass. Fig. 2.6.3 Temperature effect on the glass membranes resistance.

2.6.4 NEN6411 Temperature compensation matrix

Using the NEN6411 norm
temperature compensation can
be calculated and is applicable for
many applications.

It’s used for pH compensation in

water applications using a glass-
electrode.

The calculation is valid for all strong

acids and strong bases. The main
application is in de-mineralized
water and alkalized boiler feed
water/condensate.
NEN 6411 pH Temperature Relationship for Strong Acids and Bases

The uncompensated pH value is:

10

9.5
pH at Reference Temperature

80 ºC
9

8.5
0 ºC
8

7.5
T = Tref = 25ºC
7

6.5

5.5

5
5 6 7 8 9

pH at Process Temperature

Fig. 2.6.4
www.yokogawa.com 17
 2.7 Isolation resistance
In view of the relatively high
resistance of the pH sensitive
glass membrane, it is necessary
to use a analyzer with a high input
impedance. This impedance must
be at least a factor of 1000 higher
than the membrane resistance
(the resistance of the reference
electrode is much lower and can be
neglected).
Insulation and screening of all
cables and connections between
2. BASICS ON pH THEORY
the measuring electrode and the
analyzer must be of the highest
order. In industrial applications the
analyzer should be installed as near
2.8 Buffer solutions
Buffer solutions are needed
as an indispensable tool for
maintaining an accurate pH
measurement. Buffer solutions
are used as references points for
calibration and adjustment of pH
measurements to compensate for
aging and deterioration.
Buffer solutions are mixtures of
weak acids and the salt of these
acids with a strong base, or mixtures
of weak bases and the salt of
these bases with a strong acid.
Consequently, if the buffers are not
accurate themselves, the calibration
serves no useful purpose.
Buffers are classified in three
categories. The main difference
between the different types of buffers
is the accuracy and buffer capacity.
Compositions
Potassium trihydrogen dioxalate
(Tetroxalate)
KH3(C204)2• 2H2O
Borax Na2B407 • 10H2O
Potassium dihydrogen phosphate+
Disodium hydrogen phosphate
Na2HP04 • 2H20 + KH2P04
Potassium hydrogen phtalate
KHC8H404
18
to the electrodes as possible. At
all times the connections between
electrodes and analyzer should be
kept dry. The insulation resistance
decreases considerably when any
moisture is present.
The insulation resistance of the
reference electrode is less critical
as its resistance with respect to the
measuring liquid is much lower.
Generally, an insulation resistance
of 107W is adequate1).
The resistance between reference
electrode and liquid is usually
between 1 and 10kW at 25°C,
Primary reference buffer
These buffers are not commercial
buffers and mainly used in
metrological institutes. These
buffers show the lowest
uncertainty in pH values, ±0.003.
Standard Buffer (secondary
reference buffer)
Standard buffer solutions are
used as standards for accurate
measurements especially in
laboratories and production
of technical buffers. They are
traceable to the primary standards.
The constituents of these buffers
are defined by international
standards such as DIN19266, IEC
726 and NIST.
The uncertainty is 0.002 and 0.004
pH units (at 25°C), depending on
the buffer.
STANDARD BUFFER SOLUTIONS1)
pH Dilution value
Molarity
at 25°C
0.0496 1.679
0.00997 9.180
0.02490+ 6.865
0.02490
0.05 4.008
Note 1: N.B.S. National Bureau of Standards of the U.S.A.
Note 2,3: See appendix 2: Definitions.
depending on the type of junction.
At higher resistance values the
sensitivity of the measuring system
will be reduced and may cause an
instability of measurement.
Note 1:pH measurements in low
conductivity liquids with a
analyzer with two high input
impedances for both the glass
and the reference electrode
require a good insulation
resistance.
Technical buffer
They are commercial buffers and
used mainly for calibration of
industrial pH measurements.
The buffer values of technical buffers
are traceable to the standard buffer.
The DIN19267 defines standards for
these solutions. The uncertainty is
0.02 a pH units (at 25 °C), depending
on the buffer.
Examples of preferred buffers by
Yokogawa are shown in the table
below. Buffer solutions prepared
from these substances conform
to the recommendations of the
DIN Standards Committee and the
National Institute of Standards and
Technology (NIST). The substances
were chosen for their particular
suitability as calibration standards
for precision pH meters.
Buffer- Temp. coeff.
(pH1/2)2) capacity3) dpH/dT
+0,186 0,070 +0,0010
+0,010 0.200 +0.0082
+0.080 0.029 -0.0028
+0.052 0.016 +0.0012
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Temperature dependence
The temperature dependence of the
pH of a buffer solution is generally
specified in terms of measured
pH values at certain discrete
temperatures.
Many buffer tables are pre-
programmed in Yokogawa
Analyzers. So if during calibration
the temperature compensator
is immersed in the buffer liquid,
2.9 PERIODIC MAINTENANCE AND CALIVON OF pH SENSORS
2.9.1 Why Is Maintenance
Needed?
The selection of pH electrodes
and holders (fittings) is based on
the demands of the application
where they will be used. The desire
is to achieve an accurate, reliable
measurement with a reasonable
life expectancy while minimizing
the required routine maintenance.
When a quality pH sensor system
is undamaged, clean and properly
calibrated, it will provide a
measurement that is accurate
and reliable. This sounds simple
enough, but ensuring the system is
clean and calibrated will sometimes
involve a significant amount of
maintenance. The effect of dirty or
faulty electrodes can be anything
from slow response to completely
erroneous measurements.
Validation control chart
Upper Control Level (+10%)
Upper Warning Level (+5%)
Calibration Value
Lower Warning Level (-5%)
Lower Control Level (-10%)
Days
www.yokogawa.com
an automatic adjustment for
temperature variations will be
done. Any stated pH value is
only meaningful if the measuring
temperature is also specified.
Be Aware
Buffers with a pH above 7 are
particularly sensitive to atmospheric
CO2. Buffer showing any sign
of turbidity must be discarded
immediately.
The validiation control chart (Fig.
2.9.1) shows that frequency of
maintenance of your measurement
depends on the required accuracy.
A pH measurement was checked
daily in buffer solution without
adjustment. This chart shows
that the reading measurement is
swinging around the calibration
value. To guarantee an accuracy
of 5% you have to calibrate the
measurement at a minimum
twice a week. If accuracy of 10 %
is accepted you can prolong the
frequency to once in two weeks.
Periodic calibration is necessary to
ensure the highest measurement
accuracy. Calibration adjusts for
the aging of the sensors and the
non-recoverable changes to the
electrodes that take place.
1 3 5 7 9 11 13
For accuracy it is recommended that
a buffer should not be used for more
than a month after opening. Buffers
should be stored in tightly sealed,
preferably air-tight bottles made
of polyethene or borosilicate glass.
Buffers should not be returned to the
bottles once removed.
2. BASICS ON pH THEORY
These effects usually happen
slowly; therefore, calibration
should not be necessary more
frequently than about once a
month in typical general purpose
applications. If more frequent
calibration is needed, it is usually
because the cleaning process was
not effective, the calibration was
not well executed, the pH readings
are temperature dependent or
the wrong electrodes have been
selected. If a film remains on the
pH sensor after cleaning, then a
measuring error can be interpreted
as a need for re-calibration. Since,
these changes are reversible with
proper cleaning, it is a key step in
the maintenance process.
Note: The periodic maintenance advice
that follows is intentionally
general in nature because pH
sensor maintenance is highly
application specific.
15 17 19 21 23 25 27 29
Fig. 2.9.1 Validation control chart
19
 2.9.2 General maintenance procedure; clean – check – calibrate
Clean:
The starting point for any pH
maintenance activity is to make sure
the electrode system is properly
cleaned. A variety of cleaning
solutions can be used depending on
the coating effects of the process on
the electrodes. Typically a 5 to 10%
solution of HCl works well.
1. Rinse off the sensor in just tap
water to remove any heavy
process coating.
2. I mmerse the electrodes in the
2. BASICS ON pH THEORY
cleaning solution for 1-2 minutes,
agitating them regularly. Use a
soft brush to clean off coating
deposits without damaging the
electrode.
3. The electrodes must then be
rinsed thoroughly with tap water
to avoid contamination of the
calibration solution with the
cleaning chemicals.
Check:
Often measurement inaccuracy is
due to the process coating of the
electrodes and calibration is not
necessary, only cleaning. Therefore,
after rinsing off the cleaning solution
thoroughly with tap water, immerse
the electrodes in a buffer solution
and allow them to stabilize. Check
the reading! Rinse again and place
the electrodes in a second (different
value) solution and allow them to
stabilize. If the readings in both
cases are within e.g. +/-0.1 pH, the
2.9.3 Two-point calibration
The electromotive force (EMF)
of a pH sensor under ideal
conditions is expressed by line
“3” in Figure 2.9.3. In practice,
the electrode shows the
characteristic that is expressed
by line “1” because of different
properties or aging of the
pH sensor. To correct this, a
zero adjustment (asymmetry
potential adjustment) and a
span adjustment (potential slope
adjustment) by the pH analyzer
re are required. First, perform a
alzero point adjustment using a
standard solution with a pH value
close to pH 7.
pH
The line is shifted from “1” to “2”
laterally so it passes through the
id zero point. Next, perform a span
ea
adjustment
l using a standard
solution with a span pH (typically
20
electrodes can be put back on line. If
not, then proceed to calibrate.
Calibrate:
A pH measurement loop requires
regular calibration of the electrodes
to compensate for their aging and
deterioration. Typically this is done
about once a month. Always use
fresh buffer solutions to avoid the
possibility of introducing errors from
contaminated or aged solutions.
Buffers supplied as liquids have a
limited shelf life, especially alkaline
buffers, which can absorb CO2 from
the air.
Yokogawa strongly recommends
to use buffer solution according
NIST or DIN standards in order to
ensure the best accuracy and best
buffer capacity is available. For most
applications we advise to doing a
two point calibration.
1. Rinse the electrodes thoroughly
with tap water to remove any
remaining cleaning solution.
Then, immerse the electrodes in
the first buffer solution (usually
the neutral buffer) and stir the
electrode for a few seconds to
ensure that the gel layer of the pH
glass membrane is completely
wet by the buffer solution and all
other fluids are removed. Then
keep the electrode still and let
the measurement stabilize. For
a good calibration, avoid any
contact of the glass membrane
pH 4 or pH 9). The slope is adjusted
so the line is rotated from “2” to “3”.
Like this, the zero point is adjusted
to pH 7 based on the EMF of a pH
Sensor voltage
1
mV 2
3
x mV
0
7 pH
with bottom of the calibration
vessel.
2. A
 djust the meter reading to the
pH value of the buffer solution
according to the method selected
(automatic or manual).
3. Rinse the electrodes with tap
water to remove the traces of
the first buffer. Then, immerse
the electrodes in the second
buffer solution (e.g. 4.01 or 9.18,
depending on the measuring
range) and repeat step 1.
Note: Alkine buffers are often inaccurate
due to absorbing CO2 during
storage after first use. So a
calibration with acidic buffers
should be preferred for all
calibrations to avoid calibration
errors due to aging of buffers.
4 Adjust the analyzer reading to the
.pH value of the buffer solution
according to the method selected
(automatic or manual).
A check for correct calibration has
to be done by immersing the sensor
again in the first buffer solution
(after rinsing) to see if the reading is
accurate. If it is not, the calibration
should be repeated.
WARNING: During calibration the
solution ground and the
temperature compensator
must be connected. The
buffer solution temperature
must be within the technical
specification limits as
indicated on the label.
sensor and the span is adjusted with
reference to the difference from pH
7 in the pH analyzer.
Fig. 2.9.3 Two-Point calibration
rea
l
id
ea
l
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2.9.4 One-point calibration

As a simple calibration method,

one-point calibration is available.
Sensor voltage
The rate of change in generated mV
EMF per pH (potential slope) of a
glass electrode is generally small
compared to that in the asymmetry x mV
potential. In one-point calibration,
the adjustment of potential slope
performed in two-point calibration
is omitted. There are two ways to
perform one-point calibration. 0
One is, as shown in Figure 2.9.4,
7 c a ca be pH
performed by using one point of an lib for
al fte
appropriate pH standard solution:

2. BASICS ON pH THEORY
ib r ra e
grab sample. The other is by using
ra tio
tio n
a sample solution being measured. n
The pH of the sample solution
is manually determined by, for
example, a portable pH analyzer,
and then the pH analyzer is adjusted
so that it reads the same pH value. Fig. 2.9.4 One-point calibration

2.9.5 Three ways to calibrate

Automatic calibration Manual calibration Sample calibration

Yokogawa analyzers offer internally
programmed buffer tables to
calculate the buffer value at
the actual temperature during
the calibration. In addition,
the stability of the reading is
automatically calculated, and when
the reading has stabilized fully
automatic adjustments of slope
and asymmetry are made. This
eliminates the question of how long
the operator should allow prior to
adjustment. A menu-driven prompt
system conducts the operator
through the simple, foolproof
routine.
Yokogawa analyzers also offer
this method, where the operator
decides the actual pH value
to enter. Manual calibration is
most often used for single-point
adjustment of the asymmetry
potential by comparison method
(grab sample). Manual calibration
can also be used to perform
a full two-point calibration
with solutions other than the
NIST buffers that are listed in
the calibration tables. In this
case, the solutions are applied
sequentially, as in the AUTOCAL
method; but the user determines
the adjustment of reading and
stability.
The operator activates the “SAMPLE”
calibration routine at the same time
as taking a representative process
sample. After determining the pH
of this sample by independent
methods, (in the lab for example)
the reading can be adjusted in
the analyzer. While the sample is
being analysed, the analyzer holds
the sample data in memory, while
continuing to control and read pH
normally.

www.yokogawa.com 21
 2.9.6 Calibration Parameters
Asymmetry Potential/Zero Point
The Asymmetry Potential (AS) also
referred to as the millivolt offset,
is an indication of the condition of
reference electrode of a pH sensor.
Theoretically when the pH sensor
is placed in same buffer like the
internal buffer (normally, pH7), the
millivolt output from the sensor
(pH and reference) should be zero.
Causes of the millivolt offset are:
• depletion of the Potassium
2. BASICS ON pH THEORY
Chloride (KCl) from the reference
electrolyte
•or the reference electrolyte
becomes poisoned with the
process solution.
When the millivolt offset is greater
than +/- 30mV, it is advisable to
replace the reference electrode. The
correction limits of the Yokogawa pH
analyzers are +/-120mV. Outside this
range an error message will appear
on the display.
Often the Zero Point instead of
Asymmetry potential is used
to indicate the condition of the
reference electrode. The Zero Point
shows the pH value when the sensor
voltage is zero.
Slope:
The Slope (SL) also referred to as
the efficiency of the pH sensor is an
indication of the condition of the
measuring (glass) electrode. The
slope is displayed in a percentage
(%) value, with 100% SL being ideal.
When the electrode is new, the slope
should be in the upper 90% range.
As the electrode ages and loses
efficiency, the slope and response of
the electrode will start to decrease.
22
500
∆pH
∆mV
mV
Asymmetry Potential
0
0 mV
-200
0
The slope value is updated each
time a two point calibration is
performed and usually only small
changes in the slope value should
be noticed. One of the main reasons
the electrode may have a low slope
value, is because it was not cleaned
before calibration, making it less
efficient. If a low slope value is
noticed, clean the electrode with
a 5-10% HCl solution for a minute,
rinse it thoroughly with clean water
and recalibrate. Depending on the
application and response time
required, it is advisable to replace
the pH electrode when the slope
value is in the mid to low 80% range.
The factory default values are 70%
- 110% of theoretical and are user
programmable from the Service
level.
When the calculated slope exceeds
the programmed values, an error
message will appear on the display.
ITP Isothermal-Point
0ºC
10ºC
25ºC
7 14
Zero
ITP Point
Null pH
Fig. 2.9.6 Calibration parameters
Reference Impedance:
The Reference Impedance (RZ) also
referred to as the resistance of the
reference junction, is an indication
of a precipitate (blockage) forming
in the reference junction and that
the electrode needs cleaning. This
resistance is also influenced by
the conductivity of the process
solution. Typically a clean reference
junction will have a resistance
of less than 10-15kΩ , but in low
conductivity solutions, RZ values
between 200 and 500 KΩ are not
uncommon. When the RZ value
starts to approach 30 -35 KΩ, the
electrode will start to have a slow
upward drift. When the reference
impedance exceeds 100 KΩ an error
message will appear on the display.
The RZ value is user programmable
between 50 - 999 KΩ.
www.yokogawa.com
 2.10 Differential Electrodes
A pH sensor measures the voltage
that the pH membrane measures
as function of the pH value of the
process sample. This voltage is then
compared with the mV output of a
reference cell that is independent
on the pH value of the sensor. In a
conventional pH measuring sensor
this reference electrode is like
described before a Metal/ Insoluble
metal salt/salt solution combination
inserted in an electrolyte solution
(or gel) that is separated from
the process with a junction. This
the process may contain ions that
poison the reference element, and
these ions penetrate the element
by diffusion especially at high
temperatures.
This means most of the problems
are not related to the pH measuring
electrode, but almost exclusively to
the reference electrode. Therefore,
the solution of the problem must
be sought in alternative ways of
generating a reference voltage
that is stable over time and is
The benefit of using a caption
reference electrode, that it has NO
junction; there is NO path from the
process to the internal element;
so NO poisoning can occur. Also
since there is NO junction, there is
NO plugging or coating problems
to worry about; and there is NO
electrolyte depletion problem
because there is NO electrolyte.

ensures that the electrolyte
composition does not vary with
process changes and that the mV
output does not change either.
However, the reference electrode
is still in open electrolytic
contact with the process and the
composition of the electrolyte
changes over time by diffusion, so
regular calibration is required. Also,
2. BASICS ON pH THEORY
independent on the pH value.
The best solution is to have a
hermetically sealed reference
electrode, like a differential
sensor. A differential sensor
still incorporates a pH sensitive
measuring element to detect ph
changes. However, for generating
a stable reference voltage now a
cation sensitive measuring element
is used.

2.10.1 Different concepts of differential sensors

Different concepts of differential process. The well-known Pfaudler

sensors are known.
One type of differential sensor uses a
second pH-sensitive glass as reference
electrode (Figure 2.10.1). This glass
membrane is installed in a pH buffer
solution. The buffer solution is
through a diaphragm connected to
the process. The reference potential is
created between the glass membrane
and buffer solution. The advantage of
the concept is that the inner reference
element will not be poisoned by earth
currents or other reasons. But the
buffer solution is still in contact with
the process and will be consumed.
PH18 sensor uses a pH sensitive and
cation sensitive enamel that are
bonded directly to the metal shaft
with no electrolyte needed. The
Pfaudler PH18 sensor is sold from
several Yokogawa affiliates.
Another example of a differential pH
sensor is the Yokogawa SC24V, which
is a 12mm combination pH glass
electrode with a salt-sensitive, glass
reference electrode membrane. The
following chapters explain how a salt-
sensitive reference works and details
the benefits.

To increase the lifetime of this buffer

solution concept, sometimes a salt
bridge will be installed between the
process and buffer solution. With this
concept longer lifetimes are possible
compared to conventional electrodes,
but there is a continuous drift of the
asymmetry potential and frequent
pH membrane calibration is still necessary.
for measurement
The other type of differential sensors
uses a salt-sensitive membrane as
a reference element to generate
chamber filled
pH membrane the reference signal. The reference
with buffer
as reference electrode is in direct contact with the
solution
Fig. 2.10.1 Differential sensor
with pH sensitive sensors

www.yokogawa.com 23
 2.10.2 How a salt-sensitive reference works, and the advantages

The SC24V (Figure 2.10.2a)

is a combined differential
pH glass sensor. The
sensor uses a reference cell
with a salt-sensitive glass
membrane. The sensor
also includes a PT1000
temperature element and
a Platinum solution ground
pin.
2. BASICS ON pH THEORY

Fig. 2.10.2a

In the past, Yokogawa developed

this glass as a single pNa- ion
sensitive electrode to measure
sensor output of pNa sensor
the sodium ion concentration 100
within a process. It was found 50
that just as a pH measurement

mV vs SCE
0
sensor, the analog signal to
the output of the reference
-50
mV

membrane follows the Nernst

-100
Law. Figure 2.10.2b. -150
-200
-250
-300
-2 0 2 4 6
pNa

Fig. 2.10.2b

However, the output voltage

of the salt-sensitive reference Potential(mV) Sensitivity reference glass for cat-ions
membrane depends on the salt 0
concentration of the sample.
-50
As it turns out, the pNa
membrane also shows sensitivity -100
Na+

to other cations, i.e. Li+, K+, and

Ca2+ (Figure 2.10.2c) within K+

a process; so the use of this

-150

reference glass is not limited Ca2+

to only sodium ions. It can be

-200
Li+
used as salt-sensitive reference
in general if the concentration
-250

is high enough and consistent

to generate a stable mV output
-300

reading.
0 1 2 3 4

Na+ K+ Li+ Ca2+ -log(Kation+)

Fig. 2.10.2c

24 www.yokogawa.com
 The graph (Figure 2.10.2d) shows
that output signal from the pH glass 500
element and the salt reference
pH glass and
element. The graph shows when
salt reference 400
the output signal of salt reference
elements
300
is stable and independent from pH glass element
changes of pH concentration and 200
can be used for pH measurement. 100

mV
0
pH
-100
600 g / l
-200
60 g / l
salt reference element

2. BASICS ON pH THEORY
6 g/ l -300
0, 6 g / l
-400
0 2 4 6 8 10 12 14 16
pH

Fig. 2.10.2d

It is important to know that the

salt-sensitive glass has sensitivity [Na+] pNa
to H+ ions. The usable range (Figure NaCl saturation level
2.10.2e) indicates the area where
the influence of H+ on the output is 1M 0
neglectable. In addition, a minimal Applicable range
Na+ concentration of 0.0001M
is required to guarantee a fast 0.01M 2
response.
0.0001M 4
0 2 4 6 8 10 12 14
pH

Fig. 2.10.2e: Application range for a salt-sensitive reference electrode in pH measurement

The following graph (Figure 2.10.2f)

Differential pH at 60 g/l NaCl
shows the sensor output of the pH
pH- SCE

membrane versus the reference

mV pNa-SCE
diff

membrane as function of the pH value

450

in a 1 mol brine solution (60 g/l NaCl).

a
400

This graph shows that in this

350
b
application the sensor behaves 300
like any normal pH sensor with the 250
Isopotential at pH 7, 0 mV and a linear
response over the complete pH range 200

down to pH 2. Below 2 pH, we see a 150

slight non-linearity. Between 0 and 1
pH, the sensor sensitivity is too low to
100

get a good measurement. 50

c
0
0 1 2 3 4 5 6 7 8
pH

Fig. 2.10.2f:
Differential pH measurement at 20Differential
ºC pH
pH- at
SCE60 g/l NaCl
pNa-SCE
mV
diff
www.yokogawa.com 450 25
400
 0
0 1 2 3 4 5 6 7 8
pH

In concentrated brine solutions

(Figure 2.10.2g) the NaCl Differential pH measurement at 20 ºC pH- SCE
concentration is much higher mV pNa-SCE

and therefore, the output of the diff

pNa electrode is different.

450

400
The sensor output is linear
over almost the complete pH
350
range with only a slight loss 300
of sensitivity below 1 pH. In
this scenario, the Asymmetry 250
Potential is now -50 mV at pH 7, 200
instead of the traditional 0 mV. In
this situation it is good practice 150
to put the ITP setting of the pH 100
analyzer to 5.6 pH to reflect
2. BASICS ON pH THEORY

the application ITP. Therefore 50

more accurate temperature
compensation is achieved and
0

the ASY is 0 mV. -50

-100
0 1 2 3 4 5 6 7 8
pH

Fig. 2.10.2g: Differential pH in concentrated brine solution

There are also applications where

the salt concentration is much mV Differential pH at 6 g/l NaCl
lower, so the following example
specifies the sensor output at 6 g/l
400

NaCl. 350

This graph (Figure 2.10.2h) shows

300

that the sensor is only linear down 250

to 3 pH and the Isopotential value
is now 8 pH, or the Asymmetry
200

Potential at pH 7 is + 60 mV. 150

These examples are showing that

100

the Asymmetry Potential or ITP 50

are different depending on the salt
concentration of the process.
0

-50
This can be seen as a problem
because in most applications this -100
concentration is not constant.
0 1 2 3 4 5 6 7

pH
However, there is no reason for
concern because a change in salt
concentration of +/- 25% only
causes an offset of 5 mV, or an
Fig. 2.10.2h: Differential pH at 6g/l NaCl

erroron the pH readings of 0,1 pH.

In most pH control applications this
will not be noticed, even when the
salt concentration varies by 25%.

26 www.yokogawa.com
2.10.3 Calibration
Normally the pH standards that are
pre-programmed in the pH analyzer
can be used for calibration, with the
pH analyzer set to “AUTOCAL”. The
SC24V however is a differential pH
sensor which needs pH buffers that
have the same ionic strength because
the sodium reference will change as
the ionic strength changes. These
pH buffers are not pre-programmed
in the pH analyzer, which means
the calibration has to be done with
specific buffer solutions and the pH
analyzer set to “MANUAL” calibration.
2.10.4 Buffer calibration
To calibrate the SC24V sensor,
two buffer solutions with known
pH values are required. It is
recommended that one buffer
solution has a value near to pH 7.00.
Depending on the process value
to be measured, the second buffer
solution should be either acidic
(below pH 7.00) or alkaline (above pH
7.00). Available buffers are: pH 2.00,
pH 4.00, pH 7.00 and pH 9.00.
The following is a very general
2-point manual calibration
procedure with buffer solution:
1. Clean the sensor using a 5%
solution of HCl;
2. R
 inse sensor thoroughly with tap
water (DO NOT use demineralized
water);
3. Immerse the sensor in the
first buffer solution (pH 7.00 is
2.10.5 Process calibration
The following is a specific one-point
manual calibration procedure for the
process to measure:
Set the pH analyzer to “MANUAL”
calibration. Wait until the pH reading
is stable.
Adjust the pH reading in the pH
analyzer to the value of the process
sample that is analysed using a
laboratory measurement. For the
laboratory measurement, we advise
a personal pH meter (e.g. Yokogawa
PH72) calibrated according to
standards (e.g. ASTM D5464, DIN
19266 or DIN 19267).
Quit the manual calibration routine
by accepting the new calculated
calibration data of zero. Slope value
will be unchanged.
www.yokogawa.com
Refer to the analyzer Instruction Manual for details.
Standard buffers can be used for functionality check of sensors, however
if they are used for calibration, the Asymmetry and Slope values will be
incorrectly calculated.
Specific buffers for sodium-based reference are available:
pH 2.00 (Ionic strength – 1 mol NaCl)
n
n pH 4.00 (Ionic strength – 1 mol NaCl)
pH 7.00 (Ionic strength – 1 mol NaCl)
n
n pH 9.00 (Ionic strength – 1 mol NaCl)
2. BASICS ON pH THEORY
recommended), stir the electrode measurement stabilize. Adjust the
for a few seconds to ensure that pH reading in the pH analyzer to
the gel layer of the pH glass the value indicated on the bottle
membrane is completely wet (in this case 4.00). Quit the manual
by buffer solution and all other calibration routine by accepting
fluids are removed. Then keep the new calculated calibration
the electrode still and let the data of zero and slope.
measurement stabilize. Adjust the After calibration, re-install the
pH reading in the pH analyzer to sensor into the process.
the value indicated on the bottle
(in this case 7.00). Go to solution 2
to do a two-point calibration;
4. Rinse sensor thoroughly with tap
water;
Note: It is important to understand it
5. Immerse the sensor in the is possible the SC24V differential
second buffer solution (pH sensor may not show the correct
4.00 is recommended), stir the pH value after buffer calibration.
electrode for a few seconds
The reason is that the ionic
strength of the buffers is 1 mol
to ensure that the gel layer NaCl, which can deviate from the
of the pH glass membrane is ionic strength of the process. For
completely wet, soaked or an accurate pH reading, an extra
1 point process calibration has
saturated by buffer solution and
to be done to compensate for
all other fluids are removed. Then differences in ionic strength.
keep the electrode still let the
mV
x mV
re
a l
0
7 pH
id
ea
l
Fig. 2.10.5: Process Calibration
27
 3. Basics on ORP
3.1. Concept of ORP
Have you ever wondered what gives
a sapphire its deep blue color?
It comes from a simple REDOX
reaction between the titanium (IV)
and iron (II) impurities. The REDOX
reaction can be seen as:
Ti4+ + Fe2+ → Ti3+ + Fe3+
However in order for the reaction
to occur energy must be supplied.
This is easily accomplished when
ordinary white light passes through
the crystals. The reaction between
the titanium and iron absorbs the
red, orange and yellow light regions
of the spectrum to fuel the REDOX
reaction, thus allowing only the blue
light to pass through the crystals,
resulting in the deep blue color seen
in sapphire crystals.
3. BASICS ON ORP
Fig. 3.1a
Fig. 3.1b
ORP (Oxidation-Reduction
Potential) is the measurement, in
millivolts, of a solution’s capacity
for electron transfer (oxidation or
reduction). ORP measurement may
also be called REDOX for REDuction
OXidation. The name reflects
that fact that within a chemical
reaction reduction and oxidation
are complementary; one cannot
occur without the other. If one
species undergoes oxidation (loses
electrons) then another species
must accept those electrons and is
said to be reduced (gains electrons).
28
With redox reactions, we speak
in terms of the strengths of the
oxidizing and reducing agents.
Oxidizing agents have the capacity
or potential to acquire electrons
and become reduced. Reduction
means the gain of electrons by an
atom, leading to a decrease in the
oxidation state of the element.
Cu2+ + 2e− → Cu
Reducing agents donate electrons
and therefore become oxidized.
Oxidation means the loss of
electrons from an atom, leading to
an increase in the oxidation state of
the element.
Fe → Fe2+ + 2e−
Since reduction and oxidation
reactions occur simultaneously, the
formulas for the two half reactions
shown above, (the reaction
between iron and copper (ii) sulfate
solution) are combined and result in
the following:
Fe + CuSO4 → FeSO4 + Cu
The Copper, Cu, acts as the
oxidizing agent while the Iron, Fe, is
the reducing agent.
Another example is the reaction
between hydrogen and fluorine in
the process of making hydrogen
fluoride (HF). The hydrogen (H2) is
being oxidized and fluorine (F2) is
reduced:
H2 + F2 → 2 HF
The two half-reactions are as
follows:
the oxidation reaction is:
H2 → 2H+ + 2 e−
and the reduction
reaction is:
F2 + 2e− → 2F−
When a chemically
inactive metal
electrode is placed
into a solution
where an oxidation-
reduction reaction
is taking place, an
electric potential Liquid being
appears at the measured
electrode. This
potential is called the
oxidation-reduction potential.
While a pH value can be obtained
within seconds, a stable ORP value
can take up to several minutes,
if not hours, to reach the final
equilibrium due to the type of
reactions and their reaction rates.
The ORP measurement behavior
is strongly influenced by the metal
surface condition. For example, a
new, unconditioned ORP electrode
will show different values than
an ORP electrode that has been
conditioned and considered in use.
3.2. The ORP Scale
A simple working definition for ORP
is a solution’s capacity for electron
transfer known as oxidation or
reduction, given in millivolts. The
measurement of ORP is the reading
of the voltage potential between
the measuring electrode and a
reference electrode. Depending on
the solution being measuring, the
ORP electrodes will serve as either
an electron donor or an electron
acceptor. ORP is similar to pH in that
pH indicates how acidic or basic a
solution is based on the hydrogen
ion activity within the solution;
and ORP indicates the reduction-
oxidation status of a solution based
on the collective electron activity
within the solution.
Figure 3.2 shows a section of the
typical ORP scale. The full range is
typically 1500 mV to -1500 mV.
Just like with pH, all ORP electrodes
are designed to produce 0 mV at pH
7. When we look at the pH scale, an
acid is defined as a substance that is
capable of liberating hydrogen ions
M
E KCl solution
Reference
electrode
(Ag/AgCl)
Indicating Junction
electrode
(Pt or Au)
Fig. 3.1c
www.yokogawa.com
 Soda Tap Water Bottled Water
+ ORP (mV)
and a base is a substance capable of
absorbing hydrogen ions. Therefore
every acid has its complementary
base. When you look at the pH scale
at 0 mV, a solution is neutral (it is
neither acidic or alkaline); but as
you move above 0 mV, the solution
is considered to be acidic, and when
you move below 0 mV the solution is
considered alkaline or basic. Some
common liquids and their respective
ORP values are shown in Figure 3.2.
Soda is known to have a pH value
of around 2.00; ;and, as shown
here, the respective ORP value for
soda is approximately 400 mV. This
indicates that a positive mV reading
(or below a pH 7) is associated with
the charge of the Hydrogen ion, H+,
and the solution is said to be acidic.
By contrast, a negative mV (or above
pH 7) is associated with the charge
of the Hydroxyl ion, OH–, and the
solution is said to be alkaline or
basic.
An ORP system can be defined in
the same manner. Unlike pH, ORP
values are affected by all oxidizing
and reducing agents, not just acids
and bases which only influence a
pH measurement. Since ORP is the
direct measurement of electrons
in transit during Oxidation-
Reduction reactions, under oxidizing
conditions, the measuring probe
loses electrons to the solution,
which creates a positive potential; in
a reducing environment, electrons
are donated to the probe, producing
a negative potential.
Since a reducing agent is capable
of accepting an electron and an
oxidizing agent is capable of losing
an electron, it can be said that the
stronger the reducing agent the
more negative the ORP value, and
the stronger the oxidizing agent the
more positive the ORP value.
For example:
Acid Permanganate solution is
www.yokogawa.com
Vitamin C Green Tea
Fig. 3.2
strongly oxidizing. It strongly
attracts electrons from the REDOX
electrode, so the REDOX potential is
highly positive.
As strongly reducing, a Sulfite
solution would the opposite. It
pushes electrons into the electrode,
so the REDOX potential is strongly
negative.
While pH is a specific measure of
the Hydrogen ion concentration in
solution, ORP only provides relative
measures of chemicals and cannot
discriminate one from another. Even
though ORP is non-ion specific, it is
an inexpensive and useful method
for controlling and monitoring the
activity of various compounds
such as chlorine, ozone, bromine,
cyanide, chromate, and many
others.
3.3. Measuring the ORP Value
ORP is measured in milivolts (mV),
with no correction for solution
temperature. Similar to pH, ORP is
not a measurement of concentration
directly, but of activity level. ORP
is the measure of the ratio of the
activities of the oxidizing and
reducing species in a solution. The
ORP value of a particular material
results in either a positive or
negative mV output; the value is
determined by the size of the atom
of the material and the number of
electrons found in its outer electron
shell. The response speed of the
process measurement varies with
the concentration of the REDOX in
the system; higher concentrations
are faster and lower concentrations
are slower.
Once again, the German physical
chemist and physicist, Walther
Hemann Nernst found that a
potential difference occurs between
a metal object and a solution that
contains ions of the same metal,
when the object is immersed in the
Cod Liver Oil Living Water
– ORP (mV)
solution.
In electrochemistry, the Nernst
equation is an equation that can
be used (in conjunction with other
information) to determine the
equilibrium reduction potential of
a half-cell1) in an electrochemical
cell2). It can also be used to
determine the total voltage
(electromotive force) for a system.
3. BASICS ON ORP
Nernst formula:
Eh = E0 + RT/nF log A ox/A red
In which…
Eh = is the Oxidation Reduction
Potential value of the
reaction
E0 = is the standard potential
that is particular to the
reaction series and that
has a constant value, that
not is affected by Aox/Ared,
temperature, etc.
RT/nF =is the Nernst Number
A ox = is the activity of the oxidant
A red = is the activity of the
reductant
Note 1: A
 half cell is a structure that
contains a conductive electrode
and a surrounding conductive
electrolyte separated by a
naturally occurring Helmholtz
double layer. Chemical reactions
within this layer momentarily
pump electric charges between
the electrode and the electrolyte,
resulting in a potential difference
between the electrode and the
electrolyte.
Note 2: A n electrochemical cell is a
device capable of either deriving
electrical energy from chemical
reactions, or facilitating
chemical reactions through the
introduction of electrical energy.
29
 Some Standard Reduction Potentials in Aqueous Solution at 25°C

Strongest Standard Reduction

Element Reduction Half-Reaction
Oxidizing Potential E0(V)
Agent F2 F2 + 2 e- → 2 F- 2.870
Au Au3+ + 3 e- →Au 1.420
Cl2 Cl2 + 2 e- → 2 Cl- 1.358
Br2 Br2 + 2 e- → 2 Br- 1.065
Hg Hg + 2 e → Hg
2+ -
0.851
Ag Ag+ + e- → Ag 0.800
Strength of Oxidizing Agent

Strength of Reducing Agent

I2 I2 + 2 e- → 2 I- 0.535
Cu Cu2+ + 2 e- → Cu 0.340
H2 2 H+ + 2 e- → H2 0.000
Pb Pb + 2 e → Pb
2+ -
-0.126
Sn Sn2+ + 2 e- → Sn -0.136
Ni Ni2+ + 2 e- → Ni -0.230
Cd Cd2+ + 2 e- → Cd -0.403
Fe Fe2+ + 2 e- → Fe -0.409
Cr Cr + 3 e → Cr
3+ -
-0.740
Zn Zn2+ + 2 e- → Zn -0.763
Al Al3+ + 3 e- → Al -1.706
Mg Mg2+ + 2 e- → Mg -2.375
3. BASICS ON ORP

Na Na+ + e- → Na -2.710
Strongest
Ca Ca2+ + 2 e- → Ca -2.760
Reducing
K K+ + e- → Lk -2.292 Agent
Li Li+ + e- → Li -3.040

The reference point for all oxidation or reduction reactions are compared to the hydrogen ion/ hydrogen (H+/H2)
reaction, which has a standard potential, E0, of 0 mV.
Table 3.3a

2H+ + 2e - → H2

Oxidized atom free electrons reduced atom

Tables for standard potentials, E0,
as seen in Table 3.3a, for various
reactions and their half reaction
can be found in various General
Chemistry Textbook reference
materials3).
The tables are usually written as
reduction reactions, showing the
free electrons and the oxidized
atom on the left and the reduced
atom on the right hand side of the
reaction equation.
A typical industrial ORP
measurement loop is similar to
that used for pH measurement. It
includes a high input impedance
analyzer, a reference electrode,
measuring electrode, and system
ground.
The reference electrode is typically
a standard pH reference electrode,
normally, a silver/silver chloride
wire in a potassium chloride
electrolyte solution. It may be
either free flowing or gel filled.
The measuring probe is typically
platinum though some other inert
metals have been tested.
When measuring ORP an
important feature to remember
is that unlike pH, temperature
compensation is not normally
used for ORP measurements.
Temperature does have
two distinct effects on ORP
measurements. However, it is not
compensated for because:
• The isopotential point (the point
of thermal independence) of an
ORP system is only relative to
the particular redox reaction,
and therefore there is no
“standard” isopoint for the
overall ORP reaction.
• Since ORP is non-ion specific
measurement, the chemistry of
the redox reaction can be quite
complex, especially if several ionic
species involving varying numbers
of electrons transferred contribute
to the reaction/oxidation reduction
potential.
• Most ORP measurements are done
at constant temperatures, such
as in process measurement and
control.
Note 3: Oxtoby, Nachtrieb, Freeman.
1994. Chemistry Science
of Change. Philadelphia:
Saunders College Publishing.

30 www.yokogawa.com
3.4. Composition of the
Measuring Electrode
ORP/Redox is a potentiometrical
measurement of the oxidizing/
reducing power of a liquid. An ORP
measuring electrode is similar to that
of a pH measuring electrode, except
it is normally constructed of an inert
(noble) metal.
The most common metal used
is platinum. Platinum, which is
considered the standard, has
excellent chemical resistance but
suffers slightly from Chemisorption1)
of oxygen, which slows down the
measurement response time. THis
means that the surface can absorb
organic compounds and it may be
attacked by sulfides and cyanides in
strongly reducing solutions such as
solutions with redox potentials less
than -500 mV.
The oxygen bonds to the surface
in strong oxidizing solutions and
hydrogen bonds to the surface in
strongly reducing solutions. Some
anti-corrosion chemicals added to
cooling towers and pasteurization
processes perceive the electron
active surface of the platinum as
corrosion and passivates it. All of
these surface reactions can result in
slow response. Any surface coatings
Glass housing
Platinum wire
Fig. 3.4a:
Separate ORP measuring electrode
www.yokogawa.com
that insulate the platinum surface
from the solution will decrease the
speed of response.
The basic measurement principle
is that the measuring electrode will
give up electrons to an oxidant or
accept electrons from a reductant,
without interfering with the
chemical reactions that are taking
place within the solution.
The metallic electrode can be
classified into three distinct types of
ORP electrode.
i) The first consists of a metal
in contact with a solution
of the same metal ions, i.e.
a silver electrode placed
in a solution of silver
nitrate, which will develop
a potential proportional to
the silver ion activity.
ii) The second consists of a
metal electrode coated
with a sparingly soluble
salt of metal, in contact
with a solution containing
the anion of the metal salt,
i.e. a silver-silver chloride
electrode in a potassium
chloride solution.
iii) The third kind, and most
Platinium wire
band
pH Glass Ag/AgCl
housing Wire pin
Fig. 3.4b:
Combination ORP/reference electrode
common, consists of a noble
metal in contact with a
solution containing both the
oxidized and reduced forms
of an oxidation-reduction
system. This is typically a
platinum.
An ORP measuring electrode can
either be a separate electrode (as
seen in Figure 3.4a), a combination
ORP/Reference electrode (as seen in
Figure 3.4b), or a combination ORP/
pH measuring electrode (as seen in
Figure 3.4c). The choice depends on
the application as well as customer
installation requirements.
Note 1: Chemisorption (or chemical
adsorption) is adsorption in
which the forces involved are
valence forces of the same
kind as those operating in
3. BASICS ON ORP
the formation of chemical
compounds.
Chemisorption means to
take up and chemically bind
(substance); in this case,
oxygen, Oxygen, onto the
surface of another substance.
Reference
system
Ag/AgCl
Wire pin
Platinum
Fig. 3.4c:
Combination ORP/pH measuring electrode
31
 3.5. Composition of the
Reference Electrode
ORP can be measured relative
to any practical or theoretical
reference electrode such as Ag/
AgCl, or SHE (Standard Hydrogen
Electrode) like described in section
2.5.2 and 2.5.5.
3.6. The Measuring Circuit
An ORP probe is really a millivolt
meter, measuring very tiny
voltages generated across a circuit
formed by a measuring electrode
(the positive pole of the circuit
normally platinum), and a reference
electrode (the negative pole), with
the process solution in between.
The difference in voltage between
the two electrodes is what is
actually being measured by the
analyzer.
These voltages give us an indication
of the ability of the oxidizers or
3. BASICS ON ORP
reducers within a solution. The
speed of response varies with the
concentration of the redox system;
high concentrations are fast and
low concentrations are slow.
3.7. Standard ORP vs pH
Compensated ORP (rH)
ORP measures the ratio of the
activities of the oxidizing and
reducing species in a solution.
This is a measure of the solution's
ability to oxidize or reduce another
substance. As an oxidizer is
added to the process, it “steals”
electrons from the surface of the
ORP measuring electrode, causing
it to become more positively
charged. Continuing to add oxidizer
generates a higher and higher
positive voltage. The role of an ORP
system is to measure these tiny
voltages generated across a circuit
formed by a measuring electrode
(the positive pole of the circuit,
normally platinum), and a reference
electrode (the negative pole,
reference electrode), immersed in
the solution.
ORP systems are typically rugged,
but do have some limitations.
For example, when ORP is used
with a chlorine-based sanitation
system, it will not indicate the
chlorine concentration in parts per
million. It will, however, indicate
32
Et
E3
E4
R elecrolyte
R elecrolyte
E2
E5
R membrane
R diaphragm
E1
R
liquid
Fig. 3.6a
The Figures 3.6a/b shows that
following potentials are of the most
significance:
E1= Potential between the ORP
metal surface and the process
E2= Potential between reference
electrode and the electrolyte
E3= Potential that develops at the
surface of the electrolyte and
the process
The sum total of these potential
differences is measured by the
signal convertor.
the effectiveness of the chlorine
as an oxidizer. ORP can be used to
indicate the activity of chlorine in a
solution. Since addition of chlorine
increases the oxidizing capability
of water, measurement of the ORP
provides a useful indicator of the
quantity of active chlorine present.
This is very important when the
chlorine is being used as a biocide
agent to control algae growth
in the process. One drawback,
however, is that pH changes also
affect the oxidizing potential of
the available chlorine and the
resultant ORP value.
Below a value of 1.9 pH, chlorine
exists as a diatomic molecule
(Cl2) in water. As the pH increases
above 1.9, chlorine oxidizes water
to produce HOCl and the ORP
millivolt reading will go down. As
the pH value continues to increase,
HOCl further dissociates into OCl-
above a pH of 7.3.
HOCl being more active that OCl-
has a higher ORP value. So, as
the pH increases, an ORP sensor
detects a decrease in value, which
reflects the decrease in HOCl.
Therefore, if we were using ORP
Et
Metal Pin
connected
Fig. 3.6b E3 E2 E1 to Platinum
Et =E1 + E2 + E3
It is also important that within the
analyzer being used for detection,
there must be a high impedance
(resistance) in order to measure the
very tiny voltages (or charge build
up) being generated by the constant
acceptance and giving up of electrons
on the ORP electrode.
The ideal conditions described
above cannot always be completely
realized in practice. A small potential
difference may exist in the reference
and is acceptable because most mV
changes measured for ORP within
solutions are large.
to monitor the diatomic Cl2 level,
we would have a large mV reading
to start with, but as it oxidizes with
water reacting with the Calcium
Thiosulfate to form a salt, the mV
reading would decrease.
Since ORP varies with pH changes,
as well as changes in the chlorine
levels, we must compensate for the
effects of any pH changes. This can
be done by measuring the pH and
ORP independent of one another
and then calculating the effect of
the pH change on the ORP using
formulas and graphs.
A simpler and more direct method
is to compensate for the pH changes
by replacing the standard Ag/AgCl
reference electrode normally used
with a pH measuring electrode. This
is known as pH Compensated ORP
(rH).
Since the pH measuring electrode
output changes as the pH of the
process changes, it acts as a moving
reference effectively cancelling out
any change in pH and leaving only the
mV value, which is due to changes in
diatomic chlorine (Cl2) levels.
www.yokogawa.com
3.8. Standard Maintenance and
Calibration
Maintenance and calibration for an
ORP system has similarities with
those methods and procedures
used for both pH and conductivity
systems. The problems and
maintenance procedures associated
with the ORP reference electrode,
for example, are handled the
same as they are for a pH loop.
The maintenance of the ORP
measuring electrode, however, is
handled in much the same way as a
conventional conductivity sensor.
Calibration of the ORP system is also
similar to how a conductivity loop is
calibrated.
Cleaning the measuring electrode
will improve accuracy and the
sensors response time. The
frequency of maintenance, which
includes cleaning and calibration,
is determined by how the process
affects the electrode. Methanol,
isopropyl alcohol or a detergent can
be used to remove oily or organic
coatings. While those applications
where removal of any anti-corrosion
chemicals or mineral deposits,
soaking the electrode in 10% nitric
acid for about 10-15 minutes is a
good starting point.
If the various forms of chemical
cleaning are not sufficient to achieve
an accurate measurement and
response time, a last resort would
be to polish the platinum surface
with a 600 grit wet-dry emery cloth
or a 1-3 micron alumina polishing
powder to remove any surface
pitting or stubborn coatings.
Reference pH 4 Buffer Solution
Electrode
20°C
68°F
Ag/AgCl 236
(1M KCl)
Ag/AgCl 257
(3M KCl)
Ag/AgCl 268
(sat. KCl)
Calomel ---
(sat. KCl)
SCE2) 223
SHE3) 470
Table 3.8a mV value of ORP solution made with pH Buffers and Quinhydrone
www.yokogawa.com
After any cleaning procedure, the
electrode should be allowed to soak
in clean tap water for at least 30
minutes to allow residual chemicals
to dissipate and the sensor to
recover. After calibration, when the
electrodes are placed back in the
process, they should be allowed to
equilibrate for at least 15 minutes.
For optimal operation, the sensors
should be installed in an area with
good agitation as process flows
past the electrode help to keep the
platinum sensing element clean.
ORP electrodes should need less
frequent calibration than a typical
pH sensor since the redox potential
is a characteristic of the interaction
between the platinum and the
redox equilibrium. However, it is
prudent to periodically verify the
performance of the measuring
system by placing the electrode in a
solution with a known potential and
calibrate as needed to correct for
the reference side of the sensor.
Standard ORP Solutions
When verification or calibration of
an ORP sensor is required, there are
two types of Standard Solutions
that are commonly used. The first
are premade solutions designed to
provide a specific stable mV value,
typically one that falls within the
process ORP range. The second type
of solutions, and probably the most
common, are those that are made
using the standard pH 4 and pH 7
buffers with quinhydrone crystals
mixed in until saturation is reached.
Either of these pH buffer solutions
can be used for calibration of an
ORP measuring system and are very
ORP Value (mV)
25°C 30°C 20°C
77°F 86°F 68°F
231 226 61
253 249 82
263 258 92
218 --- ---
218 213 47
462 454 295
practical if pH loops are also being
maintained. Preparation and use of
both types of solutions are discussed
below:
Quinhydrone1) Solution
To create an ORP solution using a
pH buffer (either 4.0 or 7.0) stir in
a small amount, approximately <
0.5 gm, of quinhydrone into 200
mls of solution. Quinhydrone is
not very soluble, so only a small
amount will dissolve in the buffer
changing the solution to an amber
color. If all of the quinhydrone
dissolves, then continue to add small
amounts and stir again. Saturation
is achieved when a small amount of
quinhydrone remains undissolved
after mixing.
Whether it is a 4.0 or a 7.0 buffer
you are using, Table 3.8a shows
the mV reading you should obtain
depending on which reference
electrode is being used. As an
3. BASICS ON ORP
example, a quinhydrone/pH 4.0
solution should give a 253 mV (± 30
mV) at 25°C for a reference electrode
that has 3M KCl internal fill.
Note 1: The quinhydrone powder
poses a moderate health risk,
causing irritation of the lungs
with prolonged exposure. The
premade calibration solutions
are fairly innocuous unless
ingested in large amounts.
Both types should be handled
carefully following good
laboratory practices.
Note 2: SCE = Saturated Calomel
Electrode
Note 3: SHE = Standard Hydrogen
Electrode
pH 7 Buffer Solution
25°C 30°C
77°F 86°F
54 47
76
70
86 79
41 ---
41 34
285 275
33
 Pre-made Stabilized ORP Solutions
Reference electrodes with different
internal fill solutions will have
different mV outputs when they
are put in the same Standard
Solution. This is because the
Standard Solution was prepared
with one specific reference fill
solution in mind. Table 9.2 lists in
the left-most column, some of the
most commonly used reference
electrode fill solutions. Across the
top of the table are the possible
reference fill solutions that Standard
Solution was prepared against. To at 25° C. This is the 250 mV value on
use the chart below, you have to the solution minus the 231 mV value
know what (1) reference solution shown as the difference between
is used in the reference electrode the SHE and the 1M KCl references.
and (2) what reference solution This would be 19 mV.
the known pre-made solution is
being compared to. For example,
if you have a pre-made 250 mV
solution that is referenced to SHE
(Standard Hydrogen Electrode)
and the reference electrode in your
measuring loop uses a 1 M KCl fill Note 1: S
 CE = Saturated Calomel
Electrode
solution, then on the transmitter
you would NOT read 250 mV, but Note 2: SHE = Standard Hydrogen
Electrode
instead you would read only 19 mV

Table 3.8b mV offset between Various Reference Electrode Solutions

ToAg/AgCI) ToAg/AgCI ToAg/AgCI)

To SCE1) To SHE2)
(3MKCI) (sat. KCI) 1M KCI)

20°C 25°C 30°C 20°C 25°C 30°C 20°C 25°C 30°C 20°C 25°C 30°C 30°C 30°C 30°C
68°F 77°F 86°F 68°F 77°F 86°F 68°F 77°F 86°F 68°F 77°F 86°F 86°F 86°F 86°F
3. BASICS ON ORP

From SCE1) – – – +34 +35 +36 +45 +45 +46 +13 +14 +16 +241 +241 +241

From Ag/
AgCI -34 -35 -36 – – – +11 +10 +9 -21 -22 -23 +205 +205 +205
(3M KCL)
FromAg/
AgCI -45 -45 -45 -11 -10 -9 – – – -32 -31 -30 +202 +199 +196
(sat KCL)
From Ag/
AgCI -13 -14 -16 +21 +22 +23 +32 +31 +30 – – – +234 +231 +228
(1M KCL)

From SHE2) -247 -244 -241 -213 -209 -205 -202 -199 -196 -234 -231 -228 – – –

Table 3.8b

Proper calibration
The following steps are commonly
used for calibration of an ORP loop.
1. Clean the ORPand Reference
electrodes FIRST.
2. M
 ake FRESH Buffer Solutions
with either Quinhydrone Crystals
(See section 3.8), or pour a fresh
sample of a pre-made stabilized
ORP solution.
A. O
 RP Buffers are best made just
before using.
B. Never keep (store) ORP
calibration solutions.
3. Perform a single (1) point If a short span is found (less than a
calibration. +150 mV change between the first
solution and the second solution),
A. P
 ick a solution with a mV value the platinum/ gold measuring
closest to the control point. surface may be coated and the
electrode should be re-cleaned and
B. If possible adjust (heat) re-calibrated.
the solution to one of the
temperatures shown in the mV
tables above.
C. Allow stabilization time then
adjust to the correct value.
4. Rinse the electrode between
calibration measurements if
checking at a second buffer value.

34 www.yokogawa.com
Notes

3. BASICS ON ORP

www.yokogawa.com 35
 4. Products and Features
Number of sensor inputs: Single or
dual sensor measurement.

The purpose of this section is to

share the benefits a customer
gains when using Yokogawa's
YOKOGAWA YOKOGAWA
Made in the Netherlands

cutting-edge technology.
It includes information on
electronics (converter/transmitter),
electrodes, and their features and
functionalities.

4.1 Electronics/ Transmitters/

Converters

A) 4–wire type analyzer:

Fig. 4.01 Control Function

(Yokogawa model: PH450G series)

Impedance monitoring: For both pH
and reference cell available (Figure
4.02, 4.03). In addition to this a
dynamic sensor checking coupled
with the wash cycle function ensure
trouble free and accurate analysis
with a minimum of maintenance.

Fig. 4.03 Impedance monitoring

Human Ma­chine Interface: High

resolution graphical display and the
touchscreen operation that make all
A-B information vis­ible to the operator.
Configuration with the touchscreen
E8 as easy as operating a Tablet P.C.
(Figure 4.04, 4.05). Choose the lan­
guage of choice (minimum of eight
languages available to choose)
4.PRODUCT & FEATURES

Type: 4-wire type

and on-screen instructions ensure
A B that the best configuration for the
Power supply: Universal AC voltage – application be obtained.
Accept range; 90 to 264 V AC Ratings;
50/60 Hz, Power Consumption; 15
VA OR Universal DC voltage accept
range 10.8 to 26.4 V DC, Power E7 E6
Consumption; 10 W

Features: Advanced temper­ature

compensation functionality,
preloaded calibration standards and
stability checks.

True multivariable analyzer: Com­

bine pH with temperature and
ORP (Redox) measurement and
all these measurements can be
utilized through the different output
functions: two mA current outputs,
four independent SPDT contact
outputs and HART®.

Full functionality: PID control on

E5 E4 E1 E2 E3
either mA output(s) or on contact
output(s) and with integral wash
function available in analyzer
(Figure 4.01).
Fig. 4.02 Stability noise rejection Fig. 4.04, 4.05 Human machine interface

Note: Not all products are offered globally

please contact local office.

36 www.yokogawa.com
Mounting: IP66/NEMA 4X 1/2DIN
enclosure for field mounting and
panel mounting
Trending: Trending display available
up to 2 weeks
Data storing: On-screen logbooks
store calibration data, configura­tion
changes and events
Input ranges: Analyzer accepts
ranges such as pH: -2 to 16 pH, ORP:
-1500 to 1500 mV, rH: 0 to 100 rH and
Temperature - Pt1000: -30 to 140ºC,
Pt100: -30 to 140ºC, 350Ω (DKK): -30
to 140ºC, 5k1: -30 to 140ºC, 6k8: -30
to 140ºC, PTC10k: -30 to 140ºC, NTC
8k55: -10 to 120ºC, 3kBalco: -30 to
140ºC.
Display: Main screen displays B) 2–Wire type analyzer:
containing primary variable in
(Yokogawa model: FLXA21 series)
large font (user selectable), other
process variable(s) in small font,
Unit symbols, Tag number (user
programmable), Process description
(user programmable), Status of
alarm output(s), Status indicator
during HOLD and WASH situation,
Main function keys.
Fig. 4.08 FLXA21 outside

Accuracy: pH input: ≤ 0.01 pH, ORP

input: ≤ 1 mV, Temperature: ≤ 0.3ºC
(≤ 0.4ºC for Pt100), Response time:
Step response is less than 4 sec for
90% (pH 7 - pH 4).
Safety Standards: In line with EN
61010-1 CSA C22.2 No.61010-1, UL
61010-1.
EMC standards: EN 61326-1 Class
A, Table 2 (For use in industrial
locations) EN 61326-2-3 EN 61000-
3-2 Class A EN 61000-3-3 Korea
Electromagnetic Conformity
Fig. 4.07 FLXA21 inside
Input circuitry: Input circuitry of
analyzer is a dual-amplifier system
with solution ground. Measuring
electrode and reference electrode
inputs amplified separately against
the solution ground contact.
Following a differential amplifier,
normal signal processing takes
place. This configuration provides
the best immunity to noise, stray
solution potentials and earth loops
No. of Sensor inputs: Single or dual
sensor measurement
Power supply: Nominal 24 V DC loop
powered system
HMI: Easy touch screen operation
and simple menu structure in
12 languages. Menus of display,
execution and setting displayed in a
selected language.
Immediate measurement: For
immediate measurement, analyzer

4.PRODUCT & FEATURES

Standard.
Ambient conditions: Handle
temperature between -20 to +55ºC
(-5 - 130ºF) and Storage temperature
-30 to +70ºC (-20 - 160ºF). Humidity
10 to 90% RH at 40ºC (100ºF) (non-
condensing).
Data protection: EEPROM for
configuration data and logbook and
Lithium cell for clock. Watchdog
timer checks microprocessor.
(Figure 4.06)
has offer quick setup functionality.
(Figure 4.02). The quick setup screen appears
when the analyzer is powered.
Features: Analyzer have
sensor diagnostics and sensor
wellness indication which make
measurement reliable.
Data store: Logbook of events and
diagnostic data available with useful
information source for maintenance.
Suitability to industrial
environment: Analyzer is designed
with the enclosure of polycarbonate
or stainless steel or stainless steel
with corrosion resistant coating.
Fig. 4.08 Prediction

Advanced temperature
compensation: Analyzer offers three
additional modes for advanced
temperature compensation viz; Full
compensation for strong acids and
alkali’s using NEN6411 algorithm,
linear temperature coefficient
setting, and Matrix temperature
compensation.

Fig. 4.06 Watchdog timer checks

www.yokogawa.com 37
 Sensor 1
Fails
Sensor 1
Alive Dead
mA output
Automatically
Sensor 2 Switch to Sensor 2
Alive
Output Signal: Bi-directional
HART digital communication
superimposed on mA (4-20mA)
signal.
Ambient conditions: Temperature
between -20 to +55ºC (-5 - 130ºF)
and storage temperature -30 to
+70ºC (-20 - 160ºF). Humidity is 10
to 95% RH at 40ºC (100ºF) (non-
condensing).
Safety Standards: In line with
EN61010-1, UL 61010-1.
EMC standards: EN61326-1 Class
A, Table 2 (For use in industrial
locations), EN61326-2-3, AS/NZS
CISPR11, Korea Electromagnetic
Conformity Standard.
ADDITIONAL POINTS DUAL
4.PRODUCT & FEATURES
SENSOR MEASUREMENTS:
Additional functionalities: Offers
calculated data function and
redundant system.
Redundant system: On the
redundant system built on two
measuring parameters of two
sensor inputs, main output
parameter automatically switched
over to the second sensor output
in case of the main sensor’s failure
condition (Figure 4.09).
HAZARDOUS AREA LOCATION:
Applicable standard:
a) ATEX Intrinsically safe approval
Applicable standards: Electrical
Apparatus for Potentially
Explosive Atmospheres in
conformity with EN 60079-
0:2009 General requirements,
EN 60079-11:2007 Intrinsic safety
“i”, EN 60079-26:2007 Equipment
with equipment protection
level (EPL) Ga, EN 60529:1992
Degrees of protection provided
38
Repair Sensor 1
Alive
Manually
Switch Back to Sensor 1
Alive
mA output
by enclosures (IP Code) Type
of protection II 1G Ex ia IIC Ga,
Group: II, Category: 1G, T4:
for ambient temperature:–20
to 55ºC, T6: for ambient
temperature:–20 to 40ºC,
Atmosphere pressure: 80kPa
(0.8bar) to 110kPa (1.1bar),
Degree of Protection of the
Enclosure: IP66.
b) IEC Ex intrinsically safe
approval Applicable standards:
IEC 60079-0: 2007 Part 0: General
requirements, IEC 60079-11:
2006 Part 11: Intrinsic safety
“i”, IEC 60079-26: 2006 Part 26:
Construction, test and marking
of Group II Zone 0 electrical
apparatus IEC 60529: 2001
Degrees of protection provided
by enclosures (IP Code), Type
of protection Ex ia IIC Ga, T4:
for ambient temperature:–20
to 55ºC, T6: for ambient
temperature:–20 to 40ºC,
Atmosphere pressure: 80kPa
(0.8bar) to 110kPa (1.1bar),
Degree of Protection of the
Enclosure: IP66.
c) FM Intrinsically safe and
nonincentive approval:
Type of protection:
Class I, Division 1, Groups A, B, C
and D (Intrinsically Safe)
Class I, Division 2, Groups A, B, C
and D (Nonincendive)
Class I, Zone 0, in Hazardous
(Classified) Locations
(Intrinsically Safe)
Class I, Zone 2, Group IIC, in
Hazardous (Classified) Locations
(Nonincendive)
AEx ia IIC
Fig. 4.09 Sensors check
Alive
mA output
Alive
For all protection type,
T4: for ambient temperature:
-20 to 55°C
 6: for ambient temperature:
T
-20 to 40°C
Atmosphere pressure: 80 kPa (0.8
bar) to 110 kPa (1.1 bar)
Degree of Protection of the
Enclosure: NEMA Type 4X and
IP66
d) CSA Intrinsically safe and
nonincentive approval:
Type of protection:
Class I, Division 1, Groups A, B, C
and D (Intrinsically Safe)
Class I, Division 2, Groups A, B, C
and D (Nonincendive)
For all protection type,
T4: for ambient temperature:
-20 to 55°C
T6: for ambient temperature:
º-20 to 40°C
Atmosphere pressure: 80 kPa (0.8
bar) to 110 kPa (1.1 bar)
Ambient Humidity: 0 to 100% (No
condensation)
Degree of Protection of the
Enclosure: Type 4X
Type of protection (E60079)
Ex ia IIC
T4: for ambient temperature:
-20 to 55°C
T6: for ambient temperature:
-20 to 40°C
Atmosphere pressure: 80 kPa (0.8
bar) to 110 kPa (1.1 bar)
Ambient Humidity: 0 to 100% (No
condensation)
Degree of Protection of the
Enclosure: IP66
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4.2. Sensors/ Electrodes
1) Combined pH/ORP sensor for
general purpose applications:
(Yokogawa model: FU20 series)
Reference system:
Long life saturated Ag/
AgCl reference system
Reference junction:
PTFE reference
diaphragm to prevent
fouling and reduce
measurement error.
Double junction
combined with ion-trap
to prolong the life of the
reference probe even in
chemically unfavorable
environments
Temperature
compensation:
Integral Pt1000
element for accurate
temperature
compensation.
Additional measurement: Equipped
with platinum ORP/LE electrode for
accurate simultaneous pH- and ORP
measurements.
Electrolyte: Polymerized electrolyte
to extend the sensors lifetime.
Construction: Wide body sensors
(26 mm diameter), holds four
separate measuring elements in one
unbreakable and chemical resistant
RytonTM or PVDF body.
Operating range:
Designed for the ranges; pH: 0 – 14,
ORP: -1500 to 1500 mV
Temperature:
- Dome Shape: -10 to 105°C
(14°F to 221°F)
- Flat Surface: 15 to 105°C
(59°Fto 221°F)
Pressure: 0 to 10 bar (0 to 142 PSIG),
Conductivity: > 50 μS/cm,
Storage temp.: -10 to 50ºC (14 to
122 °F).
www.yokogawa.com
2) Combined pH/ORP sensor
for harsh applications with
fluctuating pressure and/or
temperature:
(example: pure water applications):
(Yokogawa model: FU24 series)
Reference system: Long
life saturated Ag/AgCl
reference system.
Reference junction: PTFE
reference diaphragm
to prevent fouling and
reduce measurement
error. Double junction
combined with ion-trap
to prolong the life of the
reference probe even in
chemically unfavorable
environments.
Temperature
compensation: Integral
Pt1000 element for
accurate temperature
compensation.
Additional measurement:
Equipped with platinum
ORP/LE electrode for
accurate simultaneous
pH- and ORP measurements.
Electrolyte: Polymerized electrolyte
to extend the sensors lifetime.
Construction: The sensor body is
made with a chemical resistant
RytonTM body. By using the Bellow
system integrated in the electrode,
a strong pressure compensation
mechanism created.
The build-in bellow ensures
immediate interior pressure
equalization to the outside
pressure, making the sensor
virtually insensitive to external
pressure variations.
A slight overpressure caused by
the bellow tension prevents fluid
ingress and maintains a positive ion
flow out of the sensor.
Operating range:
Designed for the ranges; pH: 0 – 14,
ORP: -1500 to 1500 mV
Temperature:
- Dome Shape: -10 to 105°C
(14°F to 221°F)
- Flat Surface: 15 to 105°C
(59°Fto 221°F)
Pressure: 0 to 10 bar (0 to 142 PSIG),
Storage temperature.: -10 to 50ºC
(5 to 122 °F).
3) Combined pH/ORP sensor
in applications where chemical
resistance is a vital issue:
(Yokogawa model: PH20 series)
Reference system: Long life
saturated Ag/AgCl reference system
Reference junction: PTFE reference
diaphragm to prevent
fouling and reduce
measurement error.
Double junction
combined with ion-trap
to prolong the life of the
reference probe even in
chemically unfavorable
environments
Temperature
compensation: Integral
Pt1000 element for
accurate temperature
compensation.
Additional
measurement:
Equipped with platinum
ORP/LE electrode for
accurate simultaneous
pH- and ORP
measurements.
Electrolyte:
Polymerized electrolyte
4.PRODUCT & FEATURES
to extend the sensors
lifetime.
Construction: The
sensor body is
made of chemically
resistant PVDF. Sensor
compensation for
changes in the process temperature
and pressure.
The compensation panels flex
to accommodate changes in the
avoiding large differential pressures
across the diaphragm and prevents
most problems associated with the
reference junction.
Operating range:
Designed for the ranges; pH: 0 – 14,
Temperature: -10 to 105ºC (14 to
221°F),
Pressure: 0 to 10 bar (0 to 142 PSIG),
Conductivity: > 50 μS/cm,
Storage temperature.: -10 to 50ºC
(5 to 122 °F).
39
 4) pH or ORP sensor: 5) Ryton pH/ORP sensors: Wetted part materials: Body Ryton
(PPS resin), glass, titanium or
(Yokogawa model: PH87/97 series) (Yokogawa model: PH8EFP, Hastelloy C, ceramics, fluorocarbon
PH8ERP, OR8EFG, OR8ERG series) rubber or Daielperfrow rubber.
Sensor type: Retractable
Sensor body made of Ryton, a
Reference system: Long life strong engineering plastic,which b) KCl Filling Type Sensor Model:
saturated Ag/AgCl reference system has good corrosion and heat PH8EFP
with the option of a solid wood state resistance. Measuring range: pH 0
reference. (Stacked KCl impregnated
to 14
wood dicks) Design: The integrated-
sensor design simplifies Temperature: Sensor is
Reference junction: calibration with suitable for temperature
Coaxial porous standard solutions and –5 to 105 deg C
PTFE reference maintenance.
diaphragm to Pressure: Sensor
prevent fouling Replacement made handles pressure from
and reduce easy: The pH glass atmospheric pressure to
measurement error. electrode of a pH 10kPa normally and up
sensor, the platinum or to 500 kPa when using
Temperature gold electrode of a ORP medium pressure KCl
compensation: sensor and junction reserve tank.
Integral Pt1000 can be individually
element for replaced. Temperature
accurate compensation sensor:
temperature a)KCl Refillable Type Pt1000
measurements. Sensor Model:
PH8ERP Wetted part materials:
Electrolyte: KCl Body; Ryton (PPS
electrolyte to Measuring range: 2 to resin), glass, titanium or
extend the sensors 12 pH Hastelloy C, ceramics,
lifetime. teflon, fluorocarbon
Measuring temperature: rubber or Daielperfrow
Construction: rubber Cable; Chlorinated
–5 to 80 deg C
The combination polyethylene rubber
sensor (PH97) Measuring pressure: (Cable sheath)
has a wide body Atmospheric pressure to 50kPa
and holds three KCl tube is made of heat-resistant
separate measuring elements in Temperature compensation soft PVC
4.PRODUCT & FEATURES

one unbreakable and chemical sensor: Pt1000

resistant PPS 40GF (RytonTM) body.
The retractable housing (PH97) is
constructed with a titanium sheath
and 316SS compression fitting.
6) Combined pH Sensor for High problems that arise when measuring
Operating range: Designed for the Purity Water: high-purity water.
ranges; pH: 0 – 14, ORP: -5000 – 5000 (Yokogawa model: PH8EHP) Temperature compensation:
mV, Temperature: 0 to 105ºC (0 to
Compensates for the effect of fluid
221°F), Pressure: 0 to 7 bar (0 to 100 Design of holder: The dedicated
temperature.
PSIG), Flow: 3 m per second holder provides solutions to

Fig. 4.10 Combined pH Sensor for High-purity water

40 www.yokogawa.com
7) Combined pH sensor in a 12
mm design with an external
solution ground:
(Yokogawa model: SC25V series)
Sensor diameter and design: 12
mm.
SC25V
Design: Sensor design with an
external solution ground. The
design made it possible to create
a large electrolyte volume. This
increases the sensor lifetime Conductivity: Measuring in
significantly compared with pH applications from 10 μS/cm
electrodes.
Connector: Variopin connector
Material of solution ground:
Titanium Applications:
Temperature sensor: Pt1000 • SC25V-ALP25 for chemically
integration in pH compartment harsh applications and high
giving highly accurate temperature temperatures
compensation.
• SC25V-AGP25 for all general
Certification: ATEX II1G Ex ia IIC T3... purpose applications
T6 Ga
CIP: CIP and Steam cleaning
possible

Specifications combined pH electrodes with temperature + solution ground

Type Membrane Resistance pH range Temp. Pressure Reference Diaphragm Ref. Atex
in MΩ/25ºC range (ºC) range kPa liquid system
SC25V-AGP25 Universal pH-glass bulb 175-275 0-14 -10 - 80 0-1000 Oversaturated KCl Ag/AgCl (wire) PTFE Yes
SC25V-ALP25 Chem. Res. pH-glass dome 500-700 0-14 +15 - 130 0-1000 Oversaturated KCl Ag/AgCl (wire) PTFE Yes

8) Combined electrode: a) SC21-AGP24 can stand high temperatures and

temperature fluctuations.
(Yokogawa model: SC21 series) • Reference system: Ag/AgCl wire
• Reference system: Double junction
• Design: pH bulb with cage
(thickened saturated KCl-solution).
protection
The built-in salt bridge prevents
SC21-AAP26 • Electrolyte and Junction: Less poisoning of the reference system.
maintenance due to the gelled A large area PTFE junction to resist
electrolyte - thickened electrolyte fouling.
(3.3 m.) and porous PTFE.
• Glass design: Heavy duty glass
SC21-ALP26
b) SC21-AAP26 membrane for prolonged operation
in corrosive, abrasive and fouling
• Reference system: High quality Ag/ environments (withstanding traces

4.PRODUCT & FEATURES

AgCl reference system (pin) which
SC21-AGP26 can stand high temperatures and
temperature fluctuations.
• Reference system: Built-in salt
bridge to prevent poisoning of the
SC21C-AGP64 reference system.
• A large area PTFE junction to resist
fouling to a high degree.
c) SC21(C)-AGP26
• Reference system: High quality Ag/
AgCl reference system (pin) which
of HF).
d) SC21(C)-ALP26
• Design: Chemical resistant, steam-
sterilizable pH-glass.
e) SC21C-AGP64
• Reference system: Ag/AgCl wire
reference system
• Electrolyte and junction: Less
maintenance by the combination
of gelled electrolyte -3.3 m KCl
electrolyte and porous PTFE.

Specifications Combined pH Electrodes (non-flow)

Type Membrane Resistance pH range Temp. Pressure Reference Reference Diaphragm Flow
in MΩ/25ºC range (ºC) range kPa liquid system
SC21-AGP24 Universal 50 - 100 0 - 14 0 - 80 1-500 3.3 m. KCI Ag/AgCl (wire) Porous PTFE 0
pH-glass bulb Thickened Silver-silverchloride
SC21(D)-AAP26 Chem. res. pH-glass bulb 250 - 400 0 - 14 0 - 110 1-500 Oversaturated Ag/AgCl (wire) Porous PTFE 0
steam-sterilisable / bulb
3
4 KCI thickened Silver-silverchloride
SC21-ALP26 Chem. res. 500 - 900 0 - 14 10 - 120 1-500 Oversaturated Ag/AgCl (wire) Porous PTFE 0
pH-glass dome KCI thickened Silver-silverchloride
SC21-AGP26 Universal 120 - 200 0 - 14 -10 - 100 1-500 Oversaturated Ag/AgCl (wire) Porous PTFE 0
pH-glass bulb KCI thickened Silver-silverchloride
SC21-AGP64 Universal 50 - 100 0 - 14 0 - 80 1-500 3.3 m. KCI Ag/AgCl (wire) Porous PTFE 0
pH-glass bulb Thickened Silver-silverchloride

www.yokogawa.com 41
 9) Combined flow type pH
electrode:
(Yokogawa model: SC21C-AGC55)
SC21C-AGC55
Type of sensor: Flowing
electrolyte sensor uses a ceramic
reference junction
Electrolyte: 3.3 molal KCl
Application: For tough applications
where pollution of the reference
system is to be expected. Low
ionic applications where the
possitive flow of electrolyte
provides the conductivity needed
to measure pH(< 50 µS/cm)
Glass type: Heavy duty pH
sensitive glass
Reference system: Flowing reference
system for pollution resistance, and
highly stable reference potential.
Electrode connection: PG13.5
standard DIN electrode connection.
Reservoir: Use in combination with
the pressurized electrolyte reservoir
to obtain a positive flow towards the
process
10) Single glass electrode:
(Yokogawa model: SM21 series)
Two types of glass are available, as
described here:
”G” glass: This is used for the
membranes of electrodes in
processes where the nominal pH
value varies between pH0 and
pH14. Since this type of glass has
a wide application range it is also
termed “general purpose” glass.
High resistance glass for chemical
resistance. G-glass sensors for all
general applications.
“L” glass: The application of “L”
glass is for measurements in
alkaline media with high process
temperatures. Low resistance glass
for fast response and sensitivity.
L-glass sensors for high temperature
chemically harsh applications.
Design: Dimensions and design meet
the requirements of DIN 19263.
Isothermal point of intersection: pH
7 (nominal value at 0 mV).
Maximum pressure: 1000 kPa (10
bar).
Thickness of the glass membrane.
Shockproof: Bulb membrane for
general purpose. A bulb shaped
glass membrane suitable for general
purpose.
Heavy duty: This dome shaped glass
membrane is suitable for harsh and
abrasive applications.

Selection guide separate electrodes: Glass sensors

Model Code Bulb type Glass resistance T range Pressure Applications remark
(Mohm) (°C) (bar)
SM21(D)-AG2 Universal 25-50 0-80 10 light, laboratory fast response, high sensitivity
SM21(D)-AG4 shockproof 50-100 0-100 10 general Universal
SM21(D)-AG6 heavy duty 120-200 0-100 10 Harsh mechanically strong
4.PRODUCT & FEATURES

SM21(D)-AL4 shockproof 300-450 15-130 10 High Temperature T cont. ≥ 70°C, high chem. Resistance
SM21(D)-AL6 heavy duty 600-900 25-130 10 High T + abbresive T cont. ≥ 70°C, high chem. Resistance

* all pH glass sensors have a sodium error of pH 0.17 above ph=13. This is because the glass will see the Na+ ion as H+ ion.
The pH reading is lower than it is in reality.

11) Single reference electrode

(Yokogawa model: SR20 series)
Ceramic PTFE Sleeve
The selection of the correct 1 2 3
type of junction of a reference
electrode depends on the
process conditions under which
this electrode has to function.
The following junction types are
available:

1. Ceramic junction
2. PTFE junction
3. Glass sleeve capillary element

Reference electrode

• Flowing type sensors for dirty
applications or (Ultra) pure
water applications (often needs
a electrolyte reservoir)
• Non-flow type sensors for all
general applications
• Ceramic and PTFE junction:
electrolyte flows slowly into the
process. PTFE resists dirt
• Glass sleeve: very dirty applications
or for (Ultra) pure water
applications because of the larger
flow-rate.
Non-flow type
A non-flow type reference electrode
can be used for processes that
don’t contain components that
poison the reference system. The
gel-type electrodes have a large
area of porous PTFE junction for
optimal resistance against electrode
pollution.

42 www.yokogawa.com
 The SR20-AC22 electrode has
a flexible PTFE tube. Therefore SR20-AC22 SR20-AP24 SR20-AP26
this electrode can be applied
in processes with frequent G 1/4" G 1/4" G 1/4"
temperature and pressure
fluctuations. Ø 17 23 Ø 17 23 Ø 17 23
Features
• Easy maintenance
• No reference liquid wastage
• Maximum process pressure: 1000
43

kPa (10 bar)

Ø 12

• High quality Ag/AgCl reference

system (pin) which can stand high
Ø 12 Ø 12

temperatures 120 120

120
A) Additional features of types
SR20(D)-AC22
Flexible

• Temperature / pressure variation

PTFE tube

compensation.
• To be used in non-polluting fluids.
• Saturated KCl-solution (pellets). 3
• For low ionic applications and high
13

temperatures. Ø5
• Temperature range: 0 to 120ºC.
Ø 8,5
Two-phase electrode Gel-type electrode Double junction gel-type
• Diaphragm resistance (25ºC) <5kΩ.

Specifications Single Reference Electrodes (non-flow)

Type Temperature Pressure Reference Reference system Diaphragm Diaphragm
range (ºC) (bar) liquid Silver-silverchloride resistance/25ºC
SR20(D)-AC22 0 - 120 10 Saturated KCl-solution (pellets) Ag/AgCl (pin) Ceramic < 5 kOhm
SR20(D)-AP24* 0 - 80 10 Thickened KCl (3.3 m.) Ag/AgCl (pin) PTFE < 5 kOhm
SR20(D)-AP26* 0 - 80 10 Thickened KCl or KNO (3.3 m.) Ag/AgCl (pin)
3
PTFE < 5 kOhm

* In applications where high process temperature occur together with very low (<2) or very high (>12) pH levels, the lifetime is shortened.

4.PRODUCT & FEATURES

B) Additional characteristics of Flow type reference electrodes
type SR20(D)-AP24
In processes with pressure
• General purpose PTFE diaphragm variations, the composition of
electrode. the electrolyte may change as a
result of process liquid penetration
• Large PTFE diaphragm.
into the electrode. Any change in
C) A
 dditional characteristics of type composition of the electrolyte may
SR20(D)-AP26 cause a measuring error or even
poisoning of the reference system
• Double junction, thickened KNO3 of the electrode. To alleviate this
in buffer compartment. problem, the electrode with an
• Large PTFE diaphragm against integral pressure compensation
pollution. system (“Bellomatic” -type
electrode”) can be the solution.
• For applications where KCl cannot
be used.
Features
• Liquid flow output preventing
diaphragm fouling and poisoning
the reference system.
• High quality Ag/AgCl reference
system (pin) which can stand high
temperatures and temperature
fluctuations.
• Standard 3.3 m. KCl electrolyte, at
temperature above 70oC thickened
electrolyte is advised.
• Automatic compensation for
process pressure variations.
• Chemical resistant Viton Bellow
material.
• Constant flow of reference liquid,
independent of the process
pressure variations for minimal
diffusion potential.
• Suitable for pure water applications
and for polluting fluids.
• Refillable, large KCl reservoir.

Specifications Single Reference Electrodes (flow)

Type Temp. Pressure Reference Reference Diaphragm Diaphragm Flow at 25ºC
range (ºC) range liquid system resistance/25ºC
SR20(D)-AS52 0 - 100 Atmospheric KCl-solution Ag/AgCl (pin) Sleeve < 10 kOhm Max. 0.2 ml/day at
(3.3 m.) Silver-silverchloride 10 kPa overpressure
SR20(D)-AC32 0 - 120 0 - 1 MPa KCl-solution Ag/AgCl (pin) Ceramic < 10 kOhm Max. 0.5 ml/day
(3.3 m.)* Silver-silverchloride

www.yokogawa.com 43
 12) Single pNa electrode:
(Yokogawa model: SM23 series)
SR20-AC32 Unit: mm SR20-AS52 Unit: mm

The SM23 is suitable for long term,

G 1/4" G 1/4"

reliable sodium ion monitoring,

and another application is to use
Ø 17 23
Ø17 23

the pNa sensor as a reference

electrode for pH measurement
Ø 12 38 10

in combination with an analyzer Ø 24

with dual high input impedance

Ø 5 20

specification. This may save

considerable maintenance costs in Ø 24

applications where the sale content

in constant and the salt content is
constant and pH>pNa+2. 301
K1500FZ

pNa measurement is used in

Ø 12

many applications, but the most

128

frequent are found in pure water

applications, where sodium is
measured to detect carry-over
Ø 12 87

of salts in steam, leakage of salt

156

through cation filters, and leakage SR20D- SR20D-

of of salt from leaking condensers. AC32 AS52

Other applications where the pNa Wrench 17 Wrench 17

electrode is used for measurement
6
26 26

is in brine solutions. Please note PG13.5 PG13.5 SM23-AN4

that accurate measurement
requires that the pH is 2-3 units
higher than the pNa value.
Bellomatic Bellomatic

120 120

Features
Ø 12 •  hock-proof glass
S
membrane with fast Unit: mm Ø 12 SM23-AN6 Unit: mm
• Dimensions and design meet the
SM23-AN4
response.
requirements of DIN 19263.
4.PRODUCT & FEATURES

G 1/4" G 1/4"

• Temperature range 0 – 100°C. B) Additional

15 15

characteristics for
Ø 17 23

• Shockproof and heavy-duty (dome

Ø 17 23

type SM23-AN6
shaped) membranes.
• pNa range < 0 to 4 • Glass resistance @
25°C 450 - 700MΩ.
• pH 2 units higher than the pNa (pH- Ø 12

pNa>2). • Heavy-duty
Ø 12

• Na+ range is 0.0001M up to membrane 120 120

saturation. guarantees great

strength retaining the
a) A
 dditional characteristics for necessary sensitivity.
type SM23-AN4
• Especially suitable
• Glass resistance @ 25°C 100-
for the more harsh
300MΩ.
Ø 11

processes. For
Ø 11

• Suitable (Ultra-, pure-) water example brine Shock proof AN4 Heavy duty AN6
application. applications.

Specifications Single pH Glass Electrodes

Type Membrane Resistance* pH Temperature Reference system Sodium error
in MOhm/25ºC range range (ºC) 0,1 N[Na ]/25ºC +

SM23-AN4 Universal pNa-glass 100-300 * 0 - 100 Ag/AgCl (pin) n.a.

bulb (shockproof)
SM23-AN6 Universal pNa-glass 450-700 * 0 - 100 Ag/AgCl (pin) n.a.
bulb (heavy duty)
* pNa range < 0 to 4 (0.0001M up to saturation) and pH 2 units higher than the pNa (pH-pNa>2)

44 www.yokogawa.com
13) Temperature electrodes: Unit: mm Unit: mm
SM60-T1 SM60D-T2
(Yokogawa model: SM60 series)
G 1/4"
For accurate pH measurement Wrench 17

temperature compensation is Ø 17 23 26

required. Either a Pt100 or a Pt PG13.5

1000 temperature electrode can be

selected. However we recommend
to use Pt1000 sensor for more
accurate measurement.
Ø 12 Ø 12

120 120

Specifications Temperature Sensor

Type Temperature Pressure Temperature
sensor range range
SM60-T2 Pt100 0 - 1 MPa -20 - 150ºC Ø6 18
SM60-T1 Pt1000 0 - 1 MPa -20 - 150ºC

14) Differential pH Sensor: describe the sensor as pH control Output voltage: The output voltage
sensor rather than pH measuring of the sensor depends only on the
(Yokogawa model: FU20-FTS)
sensor. salt concentration of the process.
Differential electrode: The
Reference system: pNa, salt- Effect of salt: A rule of thumb is that
differential measuring principle
sensitive reference glass. The a change in salt concentration of +/-
combines the normal potential
reference is not a (liquid) junction 25% has an effect of less than 0.1pH
generated by the pH glass with the
but a glass sensor which responds on the pH reading.
potential from a Sodium pNa glass.
to the sodium level in the sample
In applications where Sodium-,
rather than to pH changes (within
Potassium- or Calcium-salt is
the applicable range of the sensor).
present the glass will generate a
stable reference voltage. This means
the measurement can be done
without a conventional reference

4.PRODUCT & FEATURES

electrode, eliminating problems
caused by aging and pollution of the
liquid junction.

The sensor responds to pH changes

rather than analyzes the accurate
pH value. In that sense it is best to
FU20-FTS

15) Differential pH sensor: Temperature sensor: Pt1000 RTD

(Yokogawa model: PH18 series)
Sensor type: Sodium Reference
Differential; can be sterilized.
Construction: Stainless rod with
pH sensitive and sodium sensitive
enamel coating
Reference system: No reference fill
solution or junction
Converter requirement: Sensor
to be used in combination with
pH meters that feature dual high
impedance inputs, adjustable
setting for iusothermal Point and
adjustable temperature coefficient.
PH18 series
pH Sensor should be made of pH
sensitive enamel and Reference
sensor be - Na+ sensitive enamel
Measuring range be 3 to 11 pH.
Sensor should be able to handle
temperature in the range of 0 to 140
ºC (284 ºF)
Sensor should be able to handle
pressure in the range of -1 to 15 Bar
Note: For accessories like cable and
fittings, please refer to detailed
specification sheets or contact
Yokogawa sales representative.

www.yokogawa.com 45
 5. Lifespan and storage of electrodes
Most customers would like to know
what the expected lifetime of a
sensor is when used under process
conditions. Customers are also
interested in the shelf life for a
sensor when stored in inventory.
Since the life of a sensor is
dependent on various parameters
like temperature, pressure, service
composition, maintenance activity
taken and sensor handling, it is
difficult to define a particular life.
Even the same application life may
vary from site to site and will vary
from application to application.
The best answer to these questions
is given by recommending
guidelines for storing and
precautions during usage of the
electrode to maximize the sensor's
lifetime.
5.1. Recommended storage
guidelines pH electrodes
Generally pH sensors consist of
a glass electrode and reference
electrode (junction), both of which
are consumable parts. Each part has
an acceptable shelf life and lifetime.
Lifetime is influenced by many
factors such as sample components,
pH value, temperature, and
pressure. Tables 5.1a and 5.1b shows
the approximate shelf time and
lifetime of various electrodes. This
is just a reference for calculating
the necessary consumable amount
when purchasing them. The
shelf time and lifetime are not
guaranteed.
Shelf life and lifetime
5. LIFESPAN & STORAGE
Shelf life is defined as the period in
OF ELECTRODES
which a product is saved as stock,
and retains its performance. That
Conditions
Part Name
Ryton body (PPS
KCl Replenish-free
resin)
type pH Sensor
(PH8ERP) Glass Electrode
KCl Refillable (P/N: K9142TN)
type pH Sensor
Junction (P/N:
(PH8EFP)
K9142TH)
46
means that proper performance
is guaranteed at first installation
of the product in process if stored
under prescribed conditions. The
proper storage conditions for each
type of sensor are mentioned in the
appropriate instruction manual. On
the box the sensor is delivered in the
acceptable storage temperature and
position is indicated by means of
pictograms.
Lifetime is defined as the time the
product shows good performance
in the processes. Because of the
variations in process conditions we
cannot be held liable for this period.
However as a guide we can state
that if the lifetime of a particular
sensor has been confirmed in mild
conditions the lifetime in more
harsh conditions will limit the life of
the sensor under such conditions.
(See Table in 5.1a)
5.2. Recommended storage
guidelines
Single pH electrode
When storing a pH sensor, the glass
electrode should be protected with
a cap containing KCl solution to
prevent performance degradation
due to drying of the glass electrode’s
glass membrane.
The sensors can be stored for
approximately two years, but
this is only a guideline and is not
guaranteed. If the moisture content
of the KCl solution evaporates,
causing the glass membrane to
become dry during this storage
period, the performance can be
restored by re-immersing the glass
electrode into KCl solution within
the two-year period.
However the proper performance of
Shelf Life
Normal Temperature/ Normal Temperature/
Pressure
3 to 5 years
2 years
2 years
the electrode has to be confirmed
by calibration as described in the
calibration chapter applicable to the
sensor type.
Single reference electrode
When a reference electrode is to
remain unused for a long period
it is necessary to fill the electrode
completely with electrolyte
solution, to close the refill opening,
and to protect the diaphragm
against drying out by fitting the
protection sleeve. This protection
sleeve must also be filled with
electrolyte solution.
Electrodes of type SR20(D)-AC32
have an inner duct (see page 43)
which contact the bellow with the
process liquid. This duct must be
sealed with the rubber plug.
With the electrodes (types SR20-
AS52) the sleeve must be loosened
and lifted. The hole in the fixed
part must be closed by means of a
protective sleeve or tape.
Combined pH sensor
To guarantee optimal performance
of combined electrodes
from Yokogawa the sensors
should be stored following the
recommendations given in the
applicable instruction manuals and
following the indications on the
exterior of the product's original
box..
In the table below the shelf life
for specific products are given,
however these periods can't be
considered guaranteed.
Table 5.1a
Lifetime
80ºC pH4 to 10
Pressure
2 to 3 years 1 to 2 years
1 month to 1
1 to 2 years
year
1 to 2 years 0.5 to 1 year
www.yokogawa.com
 Productgroup Maximum shelf life
Reference
Modelcode(s) in months
Reference-electrodes

Flowing type reference (e.g. SR20-AC32) 15 Month-code on package

Non-flowing type reference (e.g. SR20-AC22) 9 Month-code on package

Combined-electrodes

Flowing type combined electrode

15 Month-code on package
(e.g. SC21-AGC55)

Non-flowing type combined electrode

Month-code on package
(e.g. SC21(D)-AAP26)

Glass electrodes
SM21*-****(all types) 15 Month-code on package

SM23-****(all types) 15 Month-code on package

Redox (Combined) electrodes

SC29*-****(all types) 15 Month-code on package

SM29*-****(alle types) 15 Month-code on package

Four in One electrodes

FU20-****(all types) 9 Month-code on package

FU24-****(all types) 9 Month-code on package

PH20-****(all types) 9 Month-code on package

SC24V-****(all types) 15 Month-code on package

SC25V-****(all Type) 9 Month-code on package

Table 5.1b

Notes

5. LIFESPAN & STORAGE OF

ELECTRODES

www.yokogawa.com 47
 6. Troubleshooting and diagnostic
6.1 Errors resulting from
cracked membranes
A minute crack in the membrane
of a glass electrode is not always
visible to the naked eye. Frequent
shocks may give minute cracks in
the membrane with consequently
measuring errors. In this case the
analyzer reading is 0 mV and the
analyzer shows a reading of pH 7,
because most pH sensors using an
internal buffer with pH 7.
For neutralization processes
(setpoint is typically pH 7) this is
a potentially dangerous situation
for the environment and plant life.
Without additional diagnostics, the
error will not be detected.
Yokogawa uses a patented online
impedance check. The analyzer
frequently checks the impedance of
the pH membrane (and reference)
via the solution ground. In case of a
broken membrane an alarm can be
generated..
Note: For details see Chapter 4,
"Products and Features"
6.2 Fouling of the pH sensor
For industrial applications and
particularly for automatic process
measurements it is of the greatest
importance that the sensor is kept
clean.
Fouling of the glass membrane is
the most common cause of error in
any pH measuring system. As the
measured potential is generated
on the surface of the pH sensitive
glass membrane it is of the greatest
importance that these membrane
surface remains clean at all times.
When the junction becomes clogged,
contact between the reference
system in the electrode and the
process liquid will be interrupted.
This will reduce the speed of
response and may result in unstable
measurement or complete failures.
In most cases it is sufficient to clean
only the electrode before calibration.
If it is necessary to hand clean the
electrodes periodically, suitable
cleansers may be used, e.g:
• Diluted solution of hydrochloric
acid (10% HCI solution)
Deposits of hydroxides, lime etc.
can be removed by immersing the
electrode in a diluted solution of
hydrochloric acid and then rinsing
with water.
•A
 solution of water with
hydrochloric acid and pepsin
Albuminous depositions can be
removed by means of a solvent
containing: 0,5 ml concentrated
hydrochloric acid, 10 gr pepsin and
1 litre demineralized water. After
treatment the electrode should be
thoroughly rinsed with clean water.
•H
 ot water:
Depositions of oil and fat can be
removed by means of hot water.
If the result is unsatisfactory, a
domestic abrasive may be carefully
used.
But often a periodic frequent cleaning
is needed to prevent building of a layer.
In these cases automatic systems help
to reduce maintenance efforts and
help to prolong the sensor lifetime.
Afterwards you find example of
automatic cleaning methods.
• Mechanical brushing:
A brush actuated by a mechanism
electrically or pneumatically driven,
passes periodically across the
membrane.
• Jet Cleaner:
This jet cleaner gives the opportunity
to avoid build up of deposits and
consequent fouling on the sensor
by spraying water (or air) onto the
membrane of the sensor.
• Chamber:
Sensor is lifted away from process
at specified intervals and washed
in cleaning chamber. Often possible
to keep the surface of the glass
electrode clean by periodically
spraying it with a cleanser. The
cleanser used, its concentration and
the cleaning frequency, depends on
the application. Often it is necessary
to sterilize the electrodes with steam.
By means of steam the temperature
of the electrodes is kept at a certain
tempereature (e.g. over 120°C ) for a
short time.
•Ultra-sonic cleaning:
With the ultra-sonic cleaning method,
the liquid around the electrodes is
vibrated. This is preventing and/or
removing any deposit formed on the
electrodes. With this method optimal
cleaning depends on the vibration
frequency and the velocity of the
process liquid past the electrodes.

Effect of cleaning Contamination by System

Cleaning system
Cleaning system Process involved
Jet (Water/air) Brush Ultrasonic Chamber

Crystalline scale Sugar, fertilizer, soda, glass B B B A

Suspended matter, Ceramic, pulp and paper, metal, water
fiber treatment, wastewater, dairy B B B B

Viscidity Flour milling, food processing B B C A

6.TROUBLESHOOTING &

Algae, River, seawater, industrial

microorganism A B B A
wastewate
DIAGNOSTIC

Absorption deposit Metal processing/treating, wastewater

treatment (coagulation sedimentation) C AC A

Rating: A = Good B = Fair C = Poor

Note 1: W
 hen polar solvents are used for cleaning, these affect the
gel-layer and it is necessary to soak the electrode for some
hours to allow the layer to reform. When a-polar solvents are
used first re-clean the electrode with a-polar solvent and
after that soak the electrode to allow the layer to reform.
Note 2: If possible increase the flow rate of the liquid to be measured past
the electrodes. This may result in a reduction of deposit on the
electrodes (typically flow rates of 2m/sec. are necessary). This
method is particularly suitable when measuring pH in liquids
containing solids that settle out quickly.

48 www.yokogawa.com
6.3 Prevention of the reference
electrode fouling
Clogging or fouling of the reference
electrode can be prevented or
reduced by:
a.The correct choice of the junction
type for the application. In
highly polluted liquids the sleeve
junction gives better results than
the smaller ceramic capillary
type, alternatively, the reference
electrode with P.T.F.E. capillary
may be used to advantage.
b.Increasing the flow of electrolyte.
By increasing the pressure on
the electrolyte in the reference
electrode the flow will increase.
This will reduce the rate of fouling.
The reference electrode with a
flexible viton bellows provides this
feature. For applications where
the process pressure fluctuates
widely, and the chance of process
liquid penetrating some types of
reference electrodes is increased,
the “Bellomatic” electrode should
be used.
c.Cleaning (See section 6.2 for types
of cleaning)
Clogging of the junction can
be remedied by soaking the
reference electrode in 3.3 m
electrolyte solution. Slowly
increase the temperature of the
solution to a maximum 80°C and
cool down in the same solution.
This ensures that any electrolyte
that may have crystallized in the
junction will become soluble
again.
If the outside of a ceramic junction
has been fouled by the process
liquid the junction can be scoured
slightly using fine emery paper,
this increases the flow capacity.
An alternative cleaning method
is to use a suitable solvent in
which the particular solids, that
have fouled in the junc­tion, will
dissolve. The electrode should be
rinsed in clean water before use.
Note: The resistance between reference
elec-trode and the process liquid
normally lies between the reference
electrode 1 and 10 kΩ at 25°C.
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6.4 Poisoning of the reference d.An excessive formation of
electrode crystals in the electrode may
restrict the discharge, and allow
As well as the possibility of fouling,
process liquid penetration.
problems will occur if the reference
To overcome this the reference
electrode becomes poisoned.
electrode must be filled with
When the flow of electrolyte in the
an electrolyte which has a
reference electrode is insufficient,
saturation point higher than the
the composition of the electrolyte
maximum temperature of the
may change as a result of process
pro­cess liquid.
liquid penetrating the electrode.
Any change in composition
of the electrolyte, in
the electrode reference
chamber, may cause a
measuring error.
Some common causes
of reference electrode
poisoning are:
a.The reference electrode
has been allowed to run
dry allowing the process
liquid to penetrate into
the elec­trode. This
problem mainly occurs
with sleeve junction
electrodes by incorrect
treatment, lack of care
in cleaning the ground
faces, or by not re-filling
the electrode early
enough.
b.Another frequent cause
of poisoning is due to
higher than expected
process pressures
or short-term, high-
pressure fluctuations.
To alleviate this
problem the electrolyte
reservoir should be
maintained at a higher
level to increase the
electrolyte pressure.
An alternative
solution is to replace
the electrode with
an integral pressure
compensation type,
such as “Bellomatic”
(See page 43/44).
c.When a reference
electrode filled
6.TROUBLESHOOTING &
with saturated KCI
solution is placed in a
DIAGNOSTIC
process liquid, which
has a temperature
considerably lower
than that of the inner
KCI solution of the
electrode, considerable
electrolyte crystallization may Fig. 6: Salt-bridge (SB20) to prevent
occur. poisoning of the refe­rence electrode.
49
 6.5 Errors caused by damped or
electrode cable and connection
It is of the greatest importance
to protect the electrode cables
and connections from ingress of
moisture. This may reduce the
insulation resistance of the cable
connections causing a partial short
circuit and consequently an erro-
neous reading. Often it happens that
the cable is broken.
The online impedance control allows
the user to detect errors caused by
moisture or broken cable.
Note: In case of moisture problems
Yokogawa can offer easily
solutions to solve this item, like
SENCOM (SENsors with digital
COMmunication)
6.6 Errors caused by shortening
the electrode cables
Often, it is usual for installation
technicians to cut off surplus
cable lengths. This is done despite
the availability of different cable
lengths.
Notes
6.TROUBLESHOOTING &
DIAGNOSTIC
50
To prevent "inside radiation"
of disturbances, the cables are
supplied with a special layer of
graphite for screening. This layer
can be difficult to remove. It is
not uncommon to see measuring
errors (e.g. instability) due to
improper shortening and finishing
of the cable. The cause of the
measuring error was the result
of a strongly decreased isolation
resistance between the core and
screen of the electrode cable.
For the glass electrode cable, this
isolation resistance must be more
than 1,000 times the resistance
across the glass membrane.
Shortening cables is strongly
discouraged.
6.7 Interferences by stray
voltages in the liquid
In many industrial applications
the voltage potential of process
liquids is significant and cannot
be neglected when making pH
measurements. This voltage level
may be due to a number of causes,
a full study of which is too complex
to be covered in this book. It is
essential therefore, that the liquids
are grounded at the point where
the pH value is to be measured.
This can be easily achieved when
metal fittings are used. When
plastic fittings are used they should
be fitted with an solution ground
electrode of suitable metal.
6.8 Errors caused by poor
installation
When commissioning a pH
measuring system, care should be
taken that the electrode connectors
do not become wet, or fouled
with fine deposits. Particular care
should be taken if the electrodes
are removed for tests, or pressure
testing of the pipe, and are left
unprotected.
If this occurs any dirt should
be carefully removed from the
electrode connections and the
cables removed and, either
thoroughly dried, or preferably
replaced.
www.yokogawa.com
7. Frequently Asked Questions & Answers
I. RELATED TO SENSORS:
7.1. What do we do when the
shelf life of a pH sensor expires?
the sensor (singular) is defined
as the period it can be stored
without loss of functionality. It
does not mean that the sensor
is not functional after this time.
Inspection before installation is
highly recommended. If the wet
pocket still contains electrolyte
then buffer check prior to
installation. If the response in the
buffers is slow then regeneration
of the sensor is needed; follow the
instruction manual.
If the wet pocket is dry, then
there is a good possibility that the
internal reference electrolyte has
evaporated and the sensor is not
functional anymore.
7.2. What is the best sensor to
measure pH within a 0 to 20%
HCl?
Conductivity, which can reach
an accuracy of 0- 20% HCl is
Inductive Conductivity. There we
can reach an accuracy of 2% of the
conductivity. A pH sensor is not
a very good solution. The strong
acid solution tends to generate
high diffusion potentials and even
if the pH measurement is 0.1 pH
accurate (logarithmic), then the
error in concentration (linear) is
25% relative.
7.3. How can I measure salt
concentration with a pNa
electrode?
We use the pNa sensor normally
as a reference electrode for pH
measurement. It is also possible to
use this electrode as a measuring
electrode in concentrated salt
solutions.
A general rule is that a pNa sensor
only responds to pNa, when the pH
value is 2 units higher.
For example the requested range
is 1- 100 g/l NaCl. It is a logarithmic
measurement so the range really
is 1-100 g/l. The molecular weight
of NaCl is 60. The logarithm of the
minimum NaCl concentration is log
1/60 = -1.78. So the pNa value is 1.78.
It means that this range we can
measure with the pNa sensor
when the pH is higher than 4. If the
requested range is 0- 100 mg/l NaCl
then the same calculation shows
www.yokogawa.com
that the measurement can be done
only if the pH is higher than 7.
In general, conductivity is a better
and more accurate method to
measure the salt concentration.
7.4. What is an ion selective
electrode?
See question 7.3. ISE is never
selective: It just responds to changes
in the ionic concentration. This is
expressed in the specifications of
the ISE as selectivity coefficient.
7.5. What is the best sensor to
measure pH within a 0 to 20%
NaOH?
Same answer as question 7.2. In
addition, the pH sensor suffers from
high alkaline errors at values above
pH 13 (4 g/l NaOH).
7.6. What is maximum flow rate
for a pH sensor?
Typical maximum flow rate is
5 m/s. However it depends on
the application. In pure water
applications flow rates must be as low
as possible, because the sample flow
will wash out the electrolyte from the
junction. When the sensor is mounted
perpendicular to the process flow
the sensor will experience vortex
vibrations and these can seriously
shorten the lifetime.
7.7. Why do you sometime
find pH range specifications
typically 2- 12?
Every pH sensor measures under
reference conditions (atmospheric
Eh = Half Potential (Ag/AgCl in KCL) against SHE
290
270
250
230
mV
210
190
170
150
0 1
pressure, ambient temperature)
7.FREQUENTLY ASKED Q&A
accurate over the 0- 14 pH range.
However in real life with high
temperatures and fluctuation
process pressures the lifetime of the
sensor can be considerably lower
especially with gel filled reference
cells. Therefore we normally limit
the pH range for gel filled sensors to
2- 12 pH.
7.8. When I am using a flowing
sensor, what is the overhead
pressure needed?
The electrolyte must flow through
the process with a flow rate that
prevents ingress of process.
Generally an overpressure of 0.1
barg = 1 m water column is sufficient,
but it must be guaranteed at all
times. Only in case of Bellomatic you
have a constant overpressure of 0.3
barg independent on the process
pressure.
In all other cases the pressure on the
electrolyte must be higher than the
maximum process pressure: static
and dynamic pressure. The static
pressure can be estimated easily,
but the dynamic pressure is difficult
to predict. It depends on viscosity
and flow rate of the process and
the dimensions of the downstream
process piping.
7.9. How can I create a steady
flowing reference for processes
with varying pressure?
Only a Bellomatic sensor offers this
function. An alternative is regulated
pressure on the electrolyte
reservoirs, which is a costly solution.
2 3 4 5
Molar
fig.: 7.11
51
 7.10. What are the advantages
of 3.3 molar KCl ?
All pH sensor suppliers use a
7.FREQUENTLY ASKED Q&A
The viscosity of the electrolyte The sensor must be cleaned and
decreases with increasing washed carefully before being
temperature. When you have a inserted into the buffer.
Bellomatic that lasts two months

saturated or a concentrated KCl A sensor is often cleaned with

solution in the reference cell. The
advantage is that a concentrated
solution decreases the electrical
resistance of the reference cell.
The solubility of KCl in water is 238
g/l at 0ºC, which is approximately
3.3 mol/l.
Therefore the advantage of 3.3mol
is that the solution stays below
saturation when the temperature
drops. The crystals would stop the
flow and block the junction.
7.11. What happens if we
combine a measuring electrode
with 3.3 mol KCl electrolyte
with a reference electrode with
1 mol KCl in a pH sensor or vice
versa?
As in Figure 7.11, the reference
potential difference between 1 and
3.3 molar is approximately 30 mV.
The sensitivity of a pH sensor at
reference temperature is 59mV/
pH. So if you combine a measuring
cell filled with 3.3mol with a
reference cell with 1mol KCl, then
you will have an offset (asymmetry
potential) 30/59mV = 0.5 pH
approximately.
This unbalance will be solved when
the sensor is calibrated and it will
show itself as Asymmetry Potential.
7.12. What is the purpose of
high viscosity KCL solution?
Resistance value of Pt 100 sensor at various temperatures.
before it needs to be refilled at
reference temperature and you
are measuring at 80oC, then the
viscosity is only 40% of the original
value. The sensor needs to be
refilled every three weeks. his is
too much maintenance and in that
case we recommend replacing the
electrolyte with the high viscosity
electrolyte.
7.13. What is the typical lifetime
of a buffer solution and after
the bottle is open?
When the bottle is open, the
electrolyte is exposed to air. Air
contains 0.04% CO2 and this gas is
absorbed by the buffer solution as
Carbonic acid. If you expose pure
water to air, the pH will drop to
5.5 pH. It means that buffer 4 and
buffer 6.85 are not very sensitive.
The buffer quality does not degrade
strongly when the bottle is opened.
The alkaline buffers are much more
sensitive to exposure to air and the
pH will continue to drop. So the
buffer 9.18 must be kept in a closed
bottle and cannot be kept long after
opening.
7.14. How many pH analyzers
can I calibrate with the same
buffer solution?
We recommend using pH buffers
only once. If you want to use the
same buffers for more analyzers,
then you must avoid contamination
of the buffers by the sensors.
acid or with detergent to remove
the fouling or the scaling. After
this chemical cleaning it must be
washed with demineralized water.
This must be done three times
with fresh water before it can be
considered clean.
This must also be done between the
two buffer solutions.
Then you can calibrate up to 10
sensors with one set of buffers as
long as it is in a short time frame.
7.15. What is the difference
between Pt100 and Pt1000
temperature sensor and which
one is better?
Both sensors have the same
temperature function and follow
the following table; The Pt1000
values are simply a factor 10 higher.
See table under: Resistance value of Pt
100 sensor at various temperatures.
The difference with Pt100 is that the
value varies only 0.391 Ω per ºC.
If we connect the Pt100 with a pH
cable of 10 m then the resistance of
this cable will be 0.7 to 0.8 Ω, which
results in a +2 ºC measuring error on
the temperature signal.
If we connect a Pt1000 sensor,
then the sensitivity is 3.91 Ω/ºC. So
when connected to the same cable
the measuring error is only +0.2
ºC., which is good enough for pH
measurement.

ºC 0 1 2 3 4 5 6 7 8 9

0 100.000 100.391 100.781 101.172 101.562 101.953 102.343 102.733 103.123 103.513

10 103.902 104.681 104.681 105.071 105.460 105.849 106.238 106.627 107.016 107.404

20 107.793 108.181 108.570 108.958 109.346 109.734 110.122 110.509 110.897 111.284

30 111.672 112.059 112.446 112.833 113.220 113.607 113.994 114.380 114.767 115.153
Resistance in ohm

40 115.539 115.925 116.311 116.697 117.083 117.469 117.854 118.240 118.625 119.01

50 119.395 119.780 120.165 120.550 120.934 121.319 121.703 122.087 122.471 122.855

60 123.239 123.623 124.007 124.390 124.774 125.157 125.540 125.923 126.306 126.689

70 127.072 127.454 127.837 128.219 128.602 128.984 129.366 129.748 130.130 130.511

80 130.893 131.274 131.656 132.037 132.418 132.799 133.180 133.561 133.941 134.322

90 134.702 135.083 135.463 135.843 136.223 136.603 136.982 137.362 137.741 138.121

100 138.500 138.879 139.258 139.637 140.016 140.395 140.773 141.152 141.530 141.908

52 www.yokogawa.com
7.16. Can we use a glass
electrode as reference? If yes,
how and where?
When you use a glass electrode as
reference, the pH sensor is called a
differential sensor. There are three
different examples:
a:pH compensated ORP
measurement: This is the most
common example. ORP depends
on the pH value as the NERNST-
Clark equation tells us: E= RT/2F
* ln [H+]/[H2]. –log [H+] is the pH
and in the same way we define –
log[H2] as rH. Then rH= 2*Eh/59.16
+ 2.pH. It means that solutions
with equal oxidizing power (rH),
the ORP varies 59 mV at each
pH unit change; so does the pH
measurement electrode. So, if we
use a pH electrode as reference we
achieve automatic compensation
of the ORP measurement.
b:Differential pH measurement:
Some manufacturers use a pH
glass electrode in a buffer solution
and use this as a reference cell.
The output of the reference pH
cell is independent of on the pH
because it is inserted in a buffer.
The buffer is in contact with the
process through a junction. The
advantage is that the sensor is
hermetically sealed and cannot be
poisoned. The shortcoming is that
the pH buffer develops diffusion
potentials in the junction.
c:Salt based reference: This
principle we use with SC24
sensors. The reference cell
responds to changes in salt
concentrations and if it does not
respond to changes in pH value
then it is the perfect sensor.
7.17. What is a smart pH sensor
and what are the advantages?
A smart pH sensor has an amplifier
in the sensor and translates the
information into a digital signal that
is transmitted to the pH analyzer.
With the SENCOM we measure the
mV readings of the three elements
of the pH sensor plus the resistance
of the temperature element. We also
measure the impedances between
these elements and calculate pH,
ORP, and impedance values. The
smart sensor does everything a pH
amplifier does and the information
is transmitted through a serial
communication. The sensor stores
the latest calibration data and
uploads this data to the pH analyzer.
www.yokogawa.com
Advantages are:
a:The sensor can be calibrated in the
laboratory and stored. As soon as
it is connected to the pH analyzer
in the field, these calibration
constants are uploaded
automatically. No field calibration
is necessary.
b:The cabling between sensor and
analyzer is low impedance cabling,
so insensitive for noise and
humidity.
c:Due to the fact that digital signals
are transmitted, it becomes
possible to communicate over a
longer distance (up to 60 meters).
7.18. Is it possible to connect
competitive sensors with
Yokogawa analyzers?
If yes, what are the conditions?
All Yokogawa analyzers are using an
open architecture with adjustable
temperature compensation,
adjustable isopotential point,
and adjustable slope; they are
compatible with all direct pH or
ORP sensors. The only exception is
SMART sensors. If the sensor has
a built-in amplifier, it cannot be
connected.
7.19. Can I connect pH sensors
without solution ground? If
yes, how?
Yes we can, but we do not
recommend this method. A pH
sensor has typically a reference
cell that is low impedance to the
process. If the process suffers from
common mode voltages then these
voltages tend to generate ground
loop currents. These currents flow
through the path of least resistance,
which is the reference cell. This
results in measuring errors (Ohm’s
law: 1 uA through 10 kΩ is 10 mV is
0.2 pH) and damage of the reference
cell. A battery connected to an
external power source is not good!
With solution grounding the path
of least resistance is the solution
ground and the pH sensor does not
suffer from ground loop currents.
Also the Yokogawa impedance
monitoring features work properly
only when there is a solution ground
in the sensor.
If you want to connect a sensor
without a solution ground, then
you shorten out the reference cell
amplifier by jumping terminal 13
(input 2) with 14 (common voltage of
the analyzer).
7.FREQUENTLY ASKED Q&A
7.20. When should we use salt
bridge over flowing reference?
Flowing reference cell and salt
bridge have the same purpose:
to prevent diffusion through the
junction and fouling of the sensor.
Sometimes a salt bridge is easy
to retrofit an existing installation
where sensor troubles are
experienced. Keep the same
reference sensor but place it in a salt
bridge.
If the process reacts with KCL or
cannot be contaminated with KCl
you can use a salt bridge filled with
another solution like NaNO3.
In high temperature applications
the maintenance may be even
less with a salt bridge because the
reference cell is under reference
conditions. Refilling of the large
reservoir is easy and does not need
to be done frequently.
7.21. When do I choose G type
glass over L type?
G-Glass is the best general purpose
pH glass. It couples a good
chemical resistance with a wide
measuring range and relatively low
electrical impedance. L-Glass has
a better chemical resistance and is
recommended for continuous use in
high temperature processes. Under
these conditions the lifetime will
be longer and the stability better
resulting in less maintenance. The
“price” of this superior specification
is the electrical impedance. This
impedance doubles with every
decrease of temperature of 10
degrees, so when you calibrate
such a sensor in the wintertime
the response is rather slow. The
impedance on the specifications is
the impedance at 25 degrees Celsius
and it is not wise to use sensors
at temperatures where this value
exceeds 1 GΩ= 1000 MΩ.
7.22. What is the benefit of
using heavy duty glass?
Heavy duty glass is the description
of pH sensors that feature a wall
thickness of the sensitive glass
membrane of approximately 1 mm.
So all customers that consider
pH sensors as fragile will benefit
53
 from this feature. Also applications
corrosive to glass like hot alkaline
solutions with high salt content or
processes with risk of HF (Fluoride
7.FREQUENTLY ASKED Q&A
containing waters at low pH) will
benefit from heavy duty features.
7.23. What sensor should I choose
for wastewater that contains oil?
pH sensors are not suitable for
measuring pH in oily water because
the oil will generate a coating on
the pH membrane and make this
membrane insensitive.
In addition, the oil will penetrate
the liquid junction. This means that
sample preparation is necessary when
measuring oily water.
The oil is typically lighter than water
so a phase separation based on
gravity is the best solution. In open
channels it must be avoided that the
II. RELATED TO Analyzers/ CONVERTERS:
7.27. Why does the FLEXA
has 7 different options
for temperature sensor
configurations?
One of the features of EXA and
FLEXA is the open architecture:
one unit for all applications, and
one unit for all sensors. The most
common difference between
the various pH sensors is the
temperature compensator. We
want to be compatible with most
direct pH/ORP sensors on the global
market.
The following temperature
compensators are supported by
EXA/FLEXA:
Pt1000 is used by Yokogawa in
recent years
Pt100 was used by many European
manufacturers like Yokogawa, E&H,
MT and Hamilton.
5k1 is used by Yokogawa Japan in
the past
3k Balco is used by US suppliers like
ABB-TBI and Rosemount
54
sensor measures at the surface
and regular cleaning coupled with
the dynamic response diagnostic
function is recommended.
7.24. Can I improve the life of
pH sensor when I choose 225
mm electrode in place of 120
mm electrode?
Yes, that is possible because
the 225 mm sensor has more
electrolytes. So depletion by
diffusion will take a longer time.
On the other hand it is more likely
to break by mechanical load like
vibration or during (dis)assembly.
7.25. Can we mount pH sensors
upside down?
Most of the pH sensors with a glass
membrane cannot be mounted
upside down. To absorb the
8k55 is used by Honeywell-Leeds &
Northroughp
350 and 6k8 were used by
Yokogawa and PTC 10k were used
by US suppliers like Inventis-
Foxboro.
7.28. Why is backlit not
available in the 2-wire
analyzers?
The 2-wire analyzers have a range
of 4- 20 mA at a supply voltage of 16
V. That means there is only 4*16=
64 mW power available. With HART
communication and BURN-OUT
feature, there is only 50 mW. These
50 mW must power the preamplifier
and the CPU plus the display.
This leaves little room for extras like
backlight.
7.29. What is a 2-wire analyzer
and what is a 4-wire analyzer?
Which one suits your application?
This terminology only refers to the
power supply of the analyzer. It
does not have any reference to the
number of wires.
The 4-wire analyzers separate
the power supply from the
measurement output. As a
minimum we need two wires for
the power supply and two wires for
the current output of the analyzer.
The PH450 has two analog outputs,
four digital outputs, one digital
thermal expansion of the internal
buffer there is always a considerable
air bubble in the sensor.
When the sensor is mounted upside
down the reference element can
lose contact with the electrolyte.
because it inserts in the air instead
of electrolyte.
The FU24 pH sensor from Yokogawa
can be used in an upside down
application because it has a special
design with a reduced size air
bubble.
7.26. Does Yokogawa offer a
non-glass pH electrode? If not
why?
Yokogawa offers the PH3A and PH18
sensor. These two types of sensors
are non-glass and suitable for
regular CIP and SIP cycles.
input and of course the sensor input
wiring. That is why PH450 has 6
cable glands. The advantage is that
any functions are combined in one
enclosure. Local control and alarm
functions are possible. In small pH
control installations this is a cost
saving feature.
The 2-wire analyzers commonly
referred to as Analyzers combine the
wires for current output, for power
supply and digital communication.
The FLXA21 combines the power
supply with mA output and HART®
communication, all with only two
wires plus shield. The advantage
is safety (only 24VDC) and simple
installation; Just two wires
between control room and analyzer.
This is an advantage in large scale
operations where process control is
centralized in the DCS system.
www.yokogawa.com
7.30. Can we select jet cleaning
along with 2-wire analyzer?
This combination is possible with
PH201 distributor. The jet cleaning
requires a signal HOLD function and
a start wash signal. The PH201 uses
a special digital signal on the mA
wiring, so it cannot be combined
with HART communication.
It is possible to use PH201 for
chemical washing of the sensor.
The PH201 uses a digital signal on
the 2-wire line, so in that case HART
is not available. PH201 is General
Purpose only and does not have CE
and CSA approval.
7.31. In a dual input FLXA21
analyzer, how can I extract
III. COMMON (related to both sensor and analyzers) QUERIES AND ANSWERS:
7.34. What feature does an
analyzer need to connect an ion
selective electrode?
The two important features/
functions are the possibility to
change the Isopotential point
and the possibility to generate a
concentration table to have output
linear to concentration.
7.35. Can I connect an ion
selective electrode to
Flexa?
The name Ion Selective
Electrode (ISE) is incorrect
because every ISE is also
sensitive to other ions
than the one mentioned
on the specification
sheet. Take for example
the pNa electrode. This
responds to Sodium ion
concentration if the pH is
higher than pNa +2 and
if no other salt ions are
present. So the name
Ion Sensitive Electrode is
better.
IV. RELATED TO MEASUREMENTS:
7.36.Why don't the process
measurement and laboratory
measurement match?
It is not that these measurements
never match, but it is not typically
heard when they do. When they
don't match, the in-line analyzer is
naturally considered to be wrong
because the laboratory is the
reference method and the in-line
measurement is just a tool to
control the process.
www.yokogawa.com
output from the second input
module?
In a dual input FLXA21 analyzer you
can use a P&F HART® to convert the
HART® dynamic variables into current
outputs or contact outputs. The
model name is KFD2-HLC-Ex1.D.
In FLXA21 you can select which
dynamic variables you like as SV.
TV and QV: Choice for FLXA21-pH is
Temp-1; Ref imp-1; pH-2; temp-2; ref
imp-2; calculated value; redundant as
example of the flexibility of FLXA21.
Commissioning>Advanced
Setup>HART>
7.32. Can we use a pH analyzer
as a temperature analyzer? If so,
how?
Assume that this is all Okay. Then
we connect the ISE to the input
1 terminals of the FLEXA and a
reference electrode to the input 2
terminals. When we use the pNa
sensor (SM23-AN4), then we know that
the ITP is 0. (The inner buffer solution
is 1 mol/l NaCl) so we program ITP as
0 and calibrate the analyzer with a 1
mol solution (pNa= 0) and a 0.01 mol
solution (pNa= 2). The display in the
When they do not match, you must
find the reason:
1. Are both analyzers accurate? To
check this both analyzers must
be validated, not calibrated. So
you take two or three fresh buffer
solutions and measure these
solutions with both analyzers. Do
not make any adjustment. Please
take a piece of paper and write
down the values and judge the
results. If one of them is wrong
The pH sensor has an accurate
temperature sensor for temperature
compensation. With PH450 it is easy to
select one mA output for temperature.
7.FREQUENTLY ASKED Q&A
Also with FLXA21 it is possible to read
temperature as dynamic variable on
the HART converter see Q. No. 7.31.
This information is useful to
understand the pH measurement and
in the case of a bypass or extractive
measurement it is a good “flow
checker” because a good flowing
sample has a higher temperature than
when the flow rate is too low (when
the sample flow is blocked.)
So it is a diagnostic tool.
7.33. Why do we choose
differential amplifier? See Q.7.19.
FLEXA displays only known pH so we
read pNa for pH.
Assume the range of the analyzer
is requested to be 1- 100 g/l NaCl
and then the output range is -0.22
to 1.78 pNa/pH. See Q3. Now we
use the concentration mode for salt
concentration and use a 21 point
table function.
Next you define the
concentration scale. Here
the range is reversed
because the higher the
pNa value is the lower the
concentration is and you
want to have a range of
0- 100 g/l which is 0- 100
ppt (parts per thousand=
g/kg).
fig. 7.35:
linerarisation
function of analyzer
by 0.1 pH or more, then that one
needs to be calibrated. Once you
have done so, you must repeat the
validation test.
2. C
 ompare apples with apples:
The in-line measurement and the
laboratory analyzer must measure
the same sample at the same
pressure and the same temperature.
It is possible to measure at the lab
at reference temperature and the
55
 in-line measurement at process
temperature. But this can only be
done when the in-line analyzer
is properly compensated for
7.FREQUENTLY ASKED Q&A
temperature. Check this by taking
a hot sample, insert the sensor
in the hot sample and let the
sample cool down to 25 degrees.
Only when the reading remains
unchanged is there proper
temperature compensation. If
the reading changes, calculate
the change in delta pH /delta
temperature and program this
coefficient in the (FL)EXA.
3. Have reasonable expectations. If
both analyzers have an accuracy of
0.1pH, you can accept differences
in readings up to 0.2 pH.
4. Take into account properties
of the process. As an example
we take boiler feed water. This
sample is ultrapure water with
traces of ammonia or morpholine
to increase the pH. This sample
is completely unbuffered. So as
soon as it is exposed to ambient
air the pH will drop due to
absorption of carbon dioxide from
the air.
V. MAINTENANCE, SERVICE and REPAIR RELATED:
7.41. When do we recommend
automatic cleaning/calibration?
Good pH sensors only need monthly
validation, so no need to do
automatic calibration as long as the
customer has access to the sensor.
In some applications the sensor gets
fouled seriously during usage and
then automatic cleaning devices
like chemical spray unit or auto
retractable fittings can be installed
successfully.
Typical customer experience with
fully automatic auto calibration
systems is that the system needs
more maintenance than the pH
sensor used to need. Plus the
autocal procedure often results
in miscalibration of the sensors,
mixing buffers, poor washing of
calibration chamber. empty buffers
bottles.
7.42. When someone states
that a pH sensor has failed,
what details are needed for
evaluation?
When a sensor has failed, then the
following information is needed
for evaluation: model code, serial
number, application details,
56
7.37. What do you recommend
to use as a laboratory
instrument?
The PH72 is an excellent device for
validation of the process analyzer. It
is small, accurate and it allows you
to do the validation measurement
as close as possible to be able to
compare apples with apples.
7.38. How accurate is your pH
analyzer?”
Generally we state that the pH
analyzer is as accurate as you are.
With lots of care you can achieve
0.05 pH accuracy. With normal care
you achieve 0.1 pH and without care
the measuring error can be pH 0.5 or
more. More information you find in
Q7.36 and Q7.37
7.39. Is it possible to record
process and diagnostic data on
a personal computer? If so what
are the methods?
This is difficult and can only be
done through additional device
like FieldMate through HART
communication.
description of the failure, lifetime
stand time and diagnostic data
from analyzer (slope, asymmetric
potential, glass impedance,
reference impedance).
Then if it is clear from the details
that sensor needs to be sent to the
factory for investigation. Ask for
the document called “Clean Sensor
Declaration” to protect the health
and safety of our colleagues in the
laboratory. Additional relevant
information other than the queries
asked for is also helpful. For
example, provide the validation
results, or make note of what the
sensor reads in three different fresh
buffer solutions.
7.43. How can the process
reading be wrong when it is
correct in the pH buffers?
This is the well-known pH problem
that we call Diffusion Potential. If
the sensor junction is plugged, then
there is no good electrical contact
between electrolyte and process.
This results in diffusion potential
that is directly measured as error.
The chemical composition of pH
buffers is different from process
liquids. So when the junction is in
bad condition, you calibrate for this
7.40. Can pH and ORP be
measured simultaneously?
Most of our pH sensors have a
noble material solution ground
and the voltage of this is measured
independently from the voltages of
the pH cell and the reference cell.
As a result, this voltage can be
used to obtain ORP readings. The
beauty of this solution is that you
can choose with one sensor and one
(FL) EXA for pH analysis, pH and ORP
analysis and just ORP analysis.
Note: Buffered means that weak acids or
weak alkaline are in the water that
absorb ingress of acid or alkaline
contaminants. Examples are
Carbonates and Phosphates. When
such a solution is contaminated
with an acid then the pH does not
change much. This is a principle
of pH buffers. Un-buffered means
that no weak acids are in the water,
so ingress of acid will immediately
change the pH value.
error in the pH buffers, but they are
different from the process. An easy
check is to look at the diagnostic
information on the pH analyzer to
see if the Asymmetry Potential is
high or the Slope is low. Most likely,
this is the problem.
Another cause can be the infamous
ground loop current. This can be
the case when you use pH sensors
without solution grounding.
7.44. Can a reference sensor be
stored in demi-water?
Sensors that are not used need to be
stored in a solution that guarantees
that the sensor is ready for use.
When the sensor is stored in demi
water the salt will be washed-out of
the junction of the reference cell. So
it is not a good solution. Yokogawa
uses the same salt concentration in
the wet pocket as is used inside the
sensor.
For combination sensors we add
a trace of acid to keep the glass
membranes active. So the best
method is to keep the it and store the
sensor back in the wet pocket when
not in use.
www.yokogawa.com
7.45. Is there any special
consideration for pH sensor
storage & transportation?
The standard packaging is designed
for long-time storage. So it should
be used when long-term storage is
foreseen.
We experience most troubles
with storage in wintertime when
service engineers keep sensors
in the trunk of the car while the
outside temperatures are below the
minimum allowable temperature
of -10 degrees. Also we experience
sensor failures if the sensors are
shipped on airplanes that don't
have air-conditioned storage
departments..
7.46. How often do I need to
calibrate my pH system?
A general rule is that analyzers need
to be validated once per month.
Only when the validation shows that
the accuracy is out of its required
limits, calibration with buffers is
needed after cleaning of course.
After this calibration the sensors
need to be validated.
7.47. Do I need to re-calibrate
after cleaning my pH-electrode?
This is a widely spread
misconception. Sensors can be
cleaned as needed. However, they
only need calibrating after cleaning
if they do not meet the validation
requirements.
7.48. How do I calibrate to get
accurate pH and ORP readings
in the same sensor?
www.yokogawa.com
All (FL) EXA analyzers have pH value, so they cannot be used to
independent calibration routines for calibrate ORP analyzers when the
pH and for ORP. pH sensor is used as reference cell.
7.FREQUENTLY ASKED Q&A
So at first you calibrate the pH
sensor function using the autocal 7.49. What’s the best calibration
function with buffer 4.01 and set?
pH 6.87. Then you use manual
The best set is obviously the NIST
calibration for the ORP function.
set: 4.01; 6.87; 9.18. They are
The ORP calibration is normally
standards all over the world and
a one point calibration, although
formulated by Mr. Bates of the
a 2 point calibration is possible.
NBS many years ago. They couple
a high level of buffer capacity,
dilution value, and minimal junction
potential to wide availability.
All other sets are convenient for
some users but do not have the
same quality and standardization.
The 4 and 6.87 buffers are the
most stable and should be used for
calibration. The other values can be
used for validation purposes.
Proceed as normal then repeat:
Normally a quinhydrone solution
where the ORP value depends on
the type of reference cell is used
for calibration. Please understand
that when there is a pH sensor
as reference cell the value would
always be the 7.00 pH value because
this is the reference pH value (88 mV
in saturated Ag/AgCl like is used in
FU20). Commercially available ORP
buffer solutions do not specify the
57
7.FREQUENTLY ASKED Q&A
REMOVE
ELECTRODE CAP
YOKOGAWA
7.50. How to refill a bellomatic
sensor?
There are several methods
described in the manual and other
publications.
There is also an easy method that
requires only a pencil. Assuming the
customer kept the original package,
there is a rubber plug that sealed the
inner tube prior to installation:
58
Electrolyte
BELLOW DOWN
Fig. 7.50: Refill Bellomatic (SR20(D)-AC32)
Step 1: Remove the electrode cap: Step 4: Fill the sensor with the
same as first drawing in fig. 7.50. proper electrolyte leaving 3 cm from
the top without electrolyte.
Step 2: Push the bellow down with
the backside of the pencil and insert Step 5: Assemble the electrode cap.
the rubber plug in the inner tube at
the bottom of the Bellomatic.
Step 3: Remove the pencil. The
bellow will stay down if the plug is
in place.
How to refill solution in bellomatic sensor?
For more details, see the instructions on YouTube:
https://www.youtube.com/watch?v=M9-nUhWBGUM)
www.yokogawa.com
Notes

7.FREQUENTLY ASKED Q&A

www.yokogawa.com 59
 Appendix 1: Chemical Compatibility

It is the customer’s responsibility These tables should be used only The result may differ if a sample
tto decide what material to use. The as a guide with no guarantee.. The contains more than one chemical. It
material used in the sample should tables show the chemical resistance is recommended to refer to multiple
be confirmed. of material to individual chemicals. tables.

Concentration & pH Material

pH Compatibility Chart W/V (%) pH (25ºC) PVC PVDF PP PTFA 316 SS Ryton Silicone Viton EPDM
Sulfuric Acid
APPENDIX1: CHEMICAL

0.5 1.0 O O O O X O O O O
0.05 2.0 O O O O X O O O O
COMPATIBILITY

Hydrochloric Acid 0.4 1.0 O O O O X O O O O

0.04 2.0 O O O O X O O O O
Inorganic Acid

Nitric Acid 0.6 1.0 O O O O O O O O O

0.06 2.0 O O O O O * O O O
Phosphoric Acid 1.0 1.5 O O O O O O O O O
Boric Acid 0.6 5.0 * O O O * O O O O
Carbonic Acid 0.6 3.6 O O O O O O O O O
Chromic Acid 1.2 0.8 O O O O * O O O O
Sulfurous Acid 0.8 1.4 O O O O * * O O O
Acetic Acid 0.6 2.8 * * O O * O O * O
Formic Acid 0.5 2.3 * * O O O O O * O
Organic Acid

Oxalic Acid 0.9 1.0 * * * O * * O O O

Lactic Acid 0.9 2.4 * X O O O O O O O
Phenol 0.9 5.4 * O * O O O O * O
Monochloroacetic Acid 0.9 1.8 X O O O O * O * O
Calcium Hydroxide 0.2 12.4 O O O O O O O O O
Potassium Hydroxide 0.5 12.7 O O O O * O O O O
Alkali

Sodium Hydroxide 0.4 12.9 O O O O O O O O O

Ammonium Hydroxide 0.5 10.4 O O O O O O O O O
Ammonium Chloride 5 O O O O X O O O O
Acid Salt

Zinc Chloride 5 O O O O X O O O O
Iron (III) Chloride 5 O O O O X O O O O
Iron (III Nitrate) 5 1.3 O O O O O O O O O
Sodium Sulfite 5 O O O O * O O O O
Sodium Carbonate 5 11.8 O O O O O O O O O
Basic
Salt

Sodium Phosphate 5 O O O O * O O O O
Potassium Chloride 5 O O O O * O O O O
Sodium Sulfate 5 O O O O * O O O O
Neutral Salt

Calcium Chloride 5 O O O O * O O O O
Sodium Nitrate 5 8.2 O O O O * O O O O
Aluminium Chloride 5 O O O O X O O O O
Hydrogen Peroxide 1 O O O O * * * O O
Organic Oxidizing

Sodium Hypochlorite 1 12.5 O O * O X * * O *

Solvent Agent

Chlorinated Lime 1 * O O O * * * O *
Potassium Dichromate 5 4.5 O O O O * O O O O
Alcohol 10 O O O O O O O * O
Organic solvent or oil
(excluding alcohol) * O * O O O * O O
Chlorinated Solvent X O X O * * * O *

O= Can be Used Notes:

*= Shortens Useful Life The recommendations of this chart are based on evaluations of
X= Cannot be Used "single components" processes. You should consult your
plant.

60 www.yokogawa.com
8. Chemical Resistance Table
This table should be used only as a guide and no guarantee is given. The table shows
Table 9-2
the(from TI 12B07A03-01E)
chemical resistance
of material to individual chemicals. The result may differ if a
sample contains more than one chemical.
: Excellent
: Good
: Not so good
X : Unusable Electrode
Holder material Ultrasonic transducer material Seal O-ring
Electrode solution ground tip material body
material
Polypropylene SUS 316 Hastelloy C Titanium Viton Ryton Remarks
Concentʼn Temp Judge Concentʼn Temp Judge Concentʼn Temp Judge Concentʼn Temp Judge Concentʼn Temp Judge

Sulfurous acid 100 20 6 30 6 30 6 30

90
5 20 5 30 X 5 30 5 30 5 30
Hydrochloric acid 5 80 5 b X 37 60

APPENDIX1: CHEMICAL
37 90 X
20 20 10 b 20 30 10 b 20 20
Chromic acid

COMPATIBILITY
Inorganic acid

20 40 X
10 20 14 30 X 15 43 20 40 5 20
Hypochlorous Acid
10 40 40 X
Hydrobromic acid 40 30 Strong acid
10 20 10 30 10 30 10 100 Weak acid 5 20
Nitric acid 60 X
10 80 10
57 20 57 25 X 57 30
Hydroiodic acid
57 70
3 20 6 30 5 30 5 30 90 20
Sulfuric acid
3 100 5 100 X 5 70 5 100 X 30 90
30 60 15 30 5 30 5 30 85 90
Phosphoric acid
30 100 5 b 5 b 5 60
15 80 10 b 10 b 10 b 15 30
Ammonia water
15 100 28 65 20 65 20 65
10 b 10 b 10 b 10 20
Potassium hydroxide
25 b 25 b 25 b 10 90
Sodium 20 80 20 30 20 30 20 30 10 20
Alkali

hydroxide 20 100 20 b 20 b 20 b Strong alkaliX 10 90

Sodium hydroxide, 100 93 Weak alkali 90
Sodium hydroxide9 to 11%
+Sodium chloride 15%
Potassium 5 b 5 b 5 b 5 b
carbonate 35 b 35 b 35 b 35 b
Sodium carbonate sat. 100 25 b 25 b 25 b 25 90
Zinc chloride 20 b 20 b 20 b
25 25 X 10 b
Aluminum chloride
25 25 X 25 b X
Ammonium chloride 35 40 25 b 25 b 25 b 25 90
Potassium chloride sat. 60 sat. 60 sat. 60 sat. 60 20 90
25 90
Chlorides

sat. 80 25 b 25 b 25 b
Calcium chloride
sat. 100
20 40 30 b X 30 b X 30 b 20 60
Ferric chloride
20 60
Sodium chloride, 20% 100 90 X 90 X 90 20
+ Saturated Cl2
(Electrolysis solution)
Seawater, Magnesium 24 24 24 24
chloride sat. 80 42 b 42 b 40 b 80
5 60 20 b 20 b 20 b 10 90 Polypropylene may
Ammonium sulfate sometimes be eroded
Nitrates Sulfates

sat. 30 sat. 30 sat. 30 by ammonium sulfate

crystals
Potassium sulfate 10 b 10 b 10 b 10 90
Sodium sulfate 20 b 20 b 20 b 10 90
Corrsion 90
20 b 20 b 20 b 10
Ammonium nitrate resistance
Sodium nitrate is good for 50 b 50 b
Sodium sulfite usual salts. 20 b 20 b
Hydrogen peroxide 10 30 10 30 10 30
30 90
Sodium sulfide 60-90 X 2 60-90 15 30 5 90
Others

2
20 80
Potassium bichromate 10 b 10 b 10 b
Sodium sulfide 60 80 10 b 10 b 10 90
Sodium bisulfate 10 b 10 b
20 30 X 30 30 20 X
Wet chlorine gas 40
60 X
Gases

Sea water + Saturated Cl2 95 X 95 95

Bromine gas 30 30 30 X
Hydrogen sulfide 20 20
80 30-90 80
Sulfurous acid gas
100
Note: "b" refers to the boiling point. T0801.EPS

TI 12B07A03-01E 1st Edition : Nov. 18,2009-00

www.yokogawa.com 61
<Toc> <Ind> <8. Chemical Resistance Table > 20

Seal O-ring Electrode

Holder material Ultrasonic transducer material body
Electrode solution ground tip material
material
Polypropylene SUS 316 Hastelloy C Titanium Viton Ryton Remarks
Concent'n Temp Judge Concent'n Temp Judge Concent'n Temp Judge Concent'n Temp Judge Concent'n Temp Judge Concent'n Temp Judge

Acetaldehyde 20 100 30 100 20

100 20 50 25
Acetone 100 25 X 100 b
100 110
100 20
Aniline 100 70 100 25 100 90
100 100
Ether 100 20 100 25 100 20
100 70 100 25
Ethylene glycol
100 100
CHEMICAL
APPENDIX CHEMICAL

96 70 100 b 100 90
Ethyl alcohol
COMPATIBILITY
COMPATIBILITY

Methyl chloride 100 20 X 100 25

100 70 100 24 X 100 20
Glacial acetic acid
100 100
Glycerin 100 70 100 25
APPENDIX1:

100 100
100 20 100 20
Chlorophenol 100 70
100 100 X
Xylene 100 20 X 100 20
100 20 X
Chlorobezene
100 100 X
Chloroform 100 20 X 100 b 100 b 100 b 100 90
100 20
100 70
Dioxane 100 90
Organic substances

100 100 X
Dichloroethare 100 70 X
100 20
Ethyl nitrate 100 105 100 90
100
Carbon tetrachloride 100 20 X 90 b 90 b 100 24 X
Trichloroethylene 100 20 X 100 b 100 b 100 b 100 90 X
Toluene 100 20 X 145 100 90
Benzophenone
100 20
Benzaldehyde 100 70 100 20
100 100 X 100 90 X
Benzyl alcohol
100 20 100 30 100 30 100 25 100 90
benzene
10 70 37 b 37 b 37 b
Fomaldehyde
10 100
Methylnaphthelen
100 20
Methyl ethyl ketone 100 90
70
Methyl alcohol 100 20 100 25 100 25
100 20 100 90 X
Nitrobenzene 100 70
100 100 X
100 20 10 b 10 b
Acetic acid 100 70
100 100 X
100 20 95 30 95 30 95 30 100 90
Phenol
100 100
Benzonic acid 100
100 20 100 20
Motor oil 100 70
100 100
Petroleum ether 100 20 100 20
100 20 101 100 20
Kerosene
100 70 X
10 40 50 100 50 100 50 100
Tartaric acid 10 60
10 80
100 70 100 25 100 180 100 180
Oil and fats
Carbon sulfide 100 20 X 100 25 100 25
Note: "b" refers to the boiling point. T0802.EPS

9.2 Reference in website

For detailed information, refer to the following site; http://www.coleparmer.com/Chemical-Resistance

62 www.yokogawa.com

TI 12B07A03-01E 1st Edition : Feb. 28,2006-00

 APPENDIX1: CHEMICAL

63
COMPATIBILITY

www.yokogawa.com
Notes
 APPENDIX 2: DEFINITIONS
Activity
The activity is a measure of the
amount of ions chemically active in a
concentration of the ions in a solution.
This means that the participation of
ions in a chemical reaction is not only
determined by the concentration but
also by the presence of other ions in the
solution. In concentrated solutions the
activity of the ions is considerably less
than the total concentration.
Activity coefficient
The activity coefficient (f) shows the
ratio between the active concentration
and the total concentration.
active concentration
f=
total concentration
An ions
An ions are negatively charged ions, e.g.
CI , N0 -, OH .
– 3 –
DEFINITIONS
APPENDIX 2:
Asymmetry potential (Easy)
This potential can exist where the
reference system is nonsymmetrical,
where differences exist in the glass
matrix at inner and outer faces, and
unbalanced diffusion potential occurs.
The asymmetry potential can be
compensated for during calibration.
Automatic temperature
compensation
Automatic control of the sensivity of the
analyzer to compensate for influence of
temperature on the electrode system.
Note: This temperature compensation
does not compensate for the
influence of temperature on the
process itself.
Buffer capacity
The buffer capacity is expressed by
the quantity of millimol equivalent of
normal hydrochloric acid required at
25°C to reduce 1 litre of buffer by 1 pH
unit, or alternatively, by the quantity
of millimol of normal caustic soda that
is required at 25°C to increase 1 litre of
buffer by 1 pH unit.
Buffer powder
Buffer powder is an accurately weighted
quantity of salts which when immersed
in a fixed quantity of distilled or
demineralized water produces a buffer
solution of constant value.
64
Buffer solution
A buffer solution is a solution with a
constant, accurate fixed pH value.
The use of this solution is necessary
to determine any deviations in the
measuring system and to allow accurate
calibration. The most important feature
of a buffer solution is that the pH value
remains constant when it is diluted with
water, acid or base.
Calomel
Calomel is an insolule salt (H92CI2) used
as part of a reference system in the
reference electrode.
Concentration
The concentration of a solution is
determined by the quantity of matter
dissolved per volume or per weight of
the solution.
Concentration units
G per litre (or kg/m3).
The weight in g per litre of solution.
Grammes (g) per kilogramme (kg)
The weight in g of matter per kg of
solution.
mg per kg
The weight in mg of matter per kg of
solution.
Note: This is commonly expressed as
p.p.m. (parts per million).
µg per kg
The weight in µg of matter per kg of
solution.
Note: This is commonly expressed
as p.p.b. (parts per billion).
Mol per litre or molar.
The weight in grammes corresponding
with the molecular weight per litre of
solution.
Mol per kg or molal
The weight in g corresponding with the
molecular weight added to 1 kg solvent.
Weight percents
The weight of a dissolved matter per 100
grammes of solution.
Diaphragm (Junction)
The diaphragm is that part of the
reference electrode which joins the
reference system in the reference
electrode with process liquid. The most
common types of diaphragm in use are: 
• Porous ceramic
• Porous teflon
• Sleeve
Dilution value
The dilution value of a buffer solution is
defined as the variation of the pH value
that occurs when the solution is diluted
with an equal volume of water.
Divalent
A divalent ion is an ion with a diva lent of
positive or negative charges.
Examples are:
AB ↔ A+B
K= [A]•[B]
[AB]
Dissociation
Dissociation is separating into positive
or negative ions.
Dissociation constant (K)
The number gives the ratio between the
concentration of the separated ions in
a matter and the concentration of the
unseparated matter.
Electrolyte
An electrolyte is a matter that separates
ions in an aqueous solution itself.
Weak electrolytes partly dissociate1).
Strong electrolytes dissociate almost
completely.
In such a solution electrical current
is conducted in equal proportions
by positive and negative ions. This is
some­times used to obtain low diffusion
potentials.
Filling liquid
The name filling liquid is often used to
describe electrolyte.
Glass electrode
A Glass electrode is a ion-specific
electrode constructed from special
types of the ion-sensitive glass. Glass
electro­des are available for sodium,
potassium, and hydrogen ions
measurement.
Hydration
Hydration is the uniting of ions with
molecules of water.
Ionization constant
See dissociation constant.
Ion strength
The strength of ions in a solution is
determined by both the concentration
of the ions in the solution and the nature
of these ions. The strength of ions
determines the activity of each ion in the
solution.
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In a equation, the strength of ions is:
C = concentration
Z = the square of the charge of the ion.
lon-specific electrode
An ion-specific electrode is an electrode
which develops an electrical potential
proportional to the logarithm of the
activity of that ion.
Isothermal point of intersection
The isothermal point of intersection
of a glass electrode is the theoretical
intersection point of the mV/pH graphs
at different temperatures. The selection
of the electrolyte in the glass electrode
determines the position of this point.
Usually this point is at pH 7 and 0 mV.
Note: The position of the isothermal point
of intersection is important for
the accuracy of the temperature
correction of the electrode system.
Monovalent
A monovalent ion contains a single
positive or negative charge (examples:
H , Na , Cl etc.).
+ + –
Nernst equation
This equation is used to determine the
potential of an ion-specific electrode. both the glass and reference electrode.
E=E0+ nF • In A
RT
E = measured potential
R = gas constant (8,314 J/mol. K) T =
absolute temperature in oK
n = valency of the ion
F = Faraday number (96493 Coulomb) In
= 2,303 log (logarithm)
A = ion activity
E0 = electro-chemical normal potential
Nernst factor
The description “Nernst factor” is
used to describe the combination of
constants in the Nernst equation. pratice.
RT 8,314 x 278
x 2,303= x 2,303 = 0,0591
nF 1 x 96493
pH electrode
An ion-specific electrode for the
measurement of the hydrogen activity in
a solution.
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pH analyzer or pH meter Standard solution
See buffer solution.
An electronic unit which converts the
potential difference between the pH
electrode and the reference electrode Solubility product
into a standard output signal. The solubility product of an electrolyte is
the product of the concentration of the
Polarization ions in a saturated solution.
Polarisation of a glass electrode takes Example:
place when it is used with a measuring
The solubility product of
instrument whose input circuit has
too low an impedance and draws an AgCI is 1,1 x 10–10.
excessive current through the pH
sensitive membrane. Strong base
A strong base is one which completely
Polyvalent dissociates:
A polyvalent ion is an ion with more than NaOH ↔ Na + OH
+ –
two positive or negative charges, e.g.
P04 3 , Cr , Fe .
– 6+ 3+
Strong acid
Reference electrode A strong acid is one which completely
dissociates:
A reference electrode is used in
HCI H + CI
+ –
combination with an ion-specific
electrode. Its function is to generate
stable poten­tials independent of Titration curve
DEFINITIONS
APPENDIX 2:
the composition of the liquid to be
The titration curve indicates the pH
measured.
curve obtained when a quantity of
reagent is added to a predetermined
Reference system
quantity of a reagent necessary to
A reference system is a combination of a neutralization a process liquid.
metal, an insoluble salt of this metal and
electrolyte. A reference system is used in Silver chloride
Silver chloride (AgCI) is an insoluble salt
used in a reference system for both glass
Response time and reference electrodes.
The response time of a glass electrode
indicates the time it takes to follow a Salt bridge
step change in pH. Usually the reponse
A salt bridge is used in applications
time is defined as the time taken to
where the electrolyte of a reference
reach 63% of the final value of a step
electrode interacts with the process. A
change.
salt bridge is a barrier solution which is
Under process conditions the response compatible with the composition of the
time of the measuring system depends process liquid.
on a number of factors versus the
positioning of the electrode in the Weak base
process stream, the reference electrode
used, etc.; and, consequently, the times A weak base only partly dissociates into
stated may not always be achieved in ions.
Example:
Cu (OH)2 Cu + + 20H .
2 –
Selectivity constant
The selectivity constant indicates Weak acid
increase in output of the ion specific
A weak acid only partly dissociates into
electrode. Concentration of strange ions
ions.
required to produce the same output as
those to which the electrode is specific. Example:
H2CO3 2H + CO3 .
+ 2–
Sensitivity
The sensitivity of a pH glass electrode is
the mV output voltage per pH change.
Theoretically, the sensitivity of a pH
electrode is 59,16 millivolts at 25°C.
65
 APPENDIX 3: LIQUID APPLICATION DATA SHEET
Please place checkmarks in the appropriate boxes and fill in the necessary information in the blanks.
Liquid Application Data Sheet [ QMQI CY C
Customer Data / General
Project/Reference Inquiry No. :

Customer TAG :

Contact Person Department:

City Street:

Telephone FAX :

e-Mail
Expected
Final Destination Month :_________ Year : __________
Delivery
needed Documention Quoted Commissioning: Yes No
(Certification ...) Services Training: Yes No
PROCESS CONDITIONS
Industry Segment Power Chemical Petrochemical Water /Waste Water

Oil/Gas Pulp & Paper Pharma Food __________

DEFINITIONS

Measuring parameter pH ORP contacting SC Ind. SC Dissolved O2

APPENDIX 2:

Process Sample Name Plant Name

Measuring Range Application

Operation Batch Continuous Monitor Control __________

Cleaning Chemical Steam Water Hotwater __________

Anticipated Issues Fouling Poisoning Coating Abrasion __________

Operating Range Min: Norm: max:

Temperature Min: Norm: max:

Pressure Min: Norm: max:

Flowrate Min: Norm: max:

Conductivity Min: Norm: max:

Composition (in %):

Solids (Types):
Concentration
Organics (Types):

Inorganics (Types):

Installation Data
Installation Indoor Outdoor Amb. Temp.: _________ Haz. Area Class.: __________ IP: ________

Mounting type Inline Bypass open tank closed tank Atline

Flow Through Immersion Retractable

Sensor fitting type Insertion T-piece with floating ball manual __________
chamber w/o floating ball automatic
Process connection ( thread/flange): _________________ Mounting : Top
Process side details
Immersion/insertion length: _________________ Side

Type cleaning system Jet Cleaning Brush Chemical /Spray Ultrasonic __________

Wetted Material 316SS Titanium PVDF/PTFE PVC PP

(Fitting/O-Ring)
Silicon Viton EPDM Kalrez __________

Analyzer Non Ex Intrinsic Non Incendive | Certification: _________ Distance to Sensor: _____

2 wire | 4 wire (24 - 30 VDC) 4 wire (80 - 240 VAC) | 4-20 mA/Hart PB FF
Remarks:

66 www.yokogawa.com
Notes

DEFINITIONS
APPENDIX 2:

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Notes

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 Notes

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 Notes

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[Ed:03] Printed in USA TI 12B00A20-01E 2017-01-2020